CN104334721A - Polysilicate-polysilicone enzyme immobilization material - Google Patents

Polysilicate-polysilicone enzyme immobilization material Download PDF

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Publication number
CN104334721A
CN104334721A CN201380028913.8A CN201380028913A CN104334721A CN 104334721 A CN104334721 A CN 104334721A CN 201380028913 A CN201380028913 A CN 201380028913A CN 104334721 A CN104334721 A CN 104334721A
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carrier
coating
enzyme
poly
immobilized enzyme
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B·兰博
A·扎克斯
T·L·布舍尔兹
D·C·鲍尔
L·E·韦伯
A·J·林德
C·M·H·杜辛
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Co2 Solutions Inc
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AKERMIN Inc
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    • C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
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    • C12N11/02—Enzymes or microbial cells immobilised on or in an organic carrier
    • C12N11/08—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer
    • C12N11/089—Enzymes or microbial cells immobilised on or in an organic carrier the carrier being a synthetic polymer obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/46—Removing components of defined structure
    • B01D53/62—Carbon oxides
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
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    • C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
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    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12Y—ENZYMES
    • C12Y402/00—Carbon-oxygen lyases (4.2)
    • C12Y402/01—Hydro-lyases (4.2.1)
    • C12Y402/01001—Carbonate dehydratase (4.2.1.1), i.e. carbonic anhydrase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D2255/80—Type of catalytic reaction
    • B01D2255/804—Enzymatic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2350/00—Pretreatment of the substrate
    • B05D2350/60—Adding a layer before coating
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The present invention relates generally to improvements in enzyme immobilization, particularly in the field of carbon dioxide capture and sequestration. It has been found that the use of sol-gel processes to immobilize enzymes in polysilicate-silicone copolymer coatings and particles and to deposit these coatings on solid supports or to use suspensions of these particles provides significant benefits for use in industrial applications involving enzyme catalysts.

Description

Polysilicates-silicone enzyme immobilization material
Invention field
The present invention relates generally to the enzyme immobilization material comprising polysilicates-silicone multipolymer.Specifically, the present invention relates to the polysilicates-silicone copolymerization immobilization material for fixing carbonic anhydrase.Immobilization carbonic anhydrase can be used for capturing carbon dioxide.
Background of invention
Developing for from industrial gas capturing carbon dioxide (CO 2) to reduce the CO in energy expenditure and air 2the technology of environmental influence.CO 2the main source of discharge comprises power station, cement kiln, natural gas processing facility, ammonia factory and hydrogen factory.The CO of trapping 2can be isolated and maybe can be used further to: improve the algal grown that oil recovery rate, processed food or acceleration can have multiple application.When natural gas processing and ammonia are produced, remove CO 2it is the required step meeting product specification.When plant hydrogen is produced, remove CO 2can plant efficiency be improved and increase output of products amount.
Current, some CO for subsequent use 2trapping technique is in each stage that business is implemented and developed.These technology comprise use amine solvent (particularly monoethanolamine-MEA) to carry out chemical absorption, physical adsorption, membrane sepn, low-temperature distillation, and the current CO being regarded as removing most of air-flow of chemical absorption that mineral carbonation amine carries out 2, especially for the low-level CO removed in Sweet natural gas 2the minimum method of cost.MEA system has more reactivity, and is therefore preferred, but in order to remove the CO of absorption from MEA 2the demand of energy high (at CO per ton 2under about 400 ten thousand BTU) and the boiler work output in power station up to about 1/3rd can be needed.
A kind of steam stripped scheme of alternative amine of appearance is that being incorporated in low year solvent exists lower specific for carbon dioxide conversion (CO 2), thus reduce regeneration energy requirement subsequently and reduce the biological catalyst of total cost.Carbonic anhydrase (CA) (EC4.2.1.1) is at occurring in nature ubiquity and has notified, with catalytic way, bicarbonate radical reversible is changed into CO 2with the enzyme family of water.
Need in this area to improve for the stability of the enzyme in the catalytic process of commercial run and improved materials, composition, method, the method and system of efficiency.
Summary of the invention
Of the present invention various among be by the material comprising polysilicates-silicone multipolymer embedding fix enzyme.
Of the present invention various among the porous particle be made up of the immobilized enzyme in polysilicates-silicone multipolymer.
Of the present invention various among be that kit contains polysilicates-silicone multipolymer and makes the porous particle of biological catalyst of hydrated carbon dioxide.Particle produces in solution and usually contains hydrophilic additive.Biological catalyst is embedded in particle composition.
Of the present invention various among be a kind of carrier of coating of the enzyme containing being fixed in the coating material comprising polysilicates-silicone multipolymer.
Of the present invention various among be a kind of carrier of coating of biological catalyst comprising solid carrier, application composition and make hydrated carbon dioxide.Application composition form layers and comprise polysilicates-silicone multipolymer and usual hydrophilic additive on the surface of solid carrier.Biological catalyst is embedded in application composition.
Of the present invention various among be if the common commercial polymeric stickers of epoxide, carbamate, resin, cyanoacrylate and methacrylic ester is in order to be adhered to the purposes of solid carrier by porous polysilicates-silicone copolymer pellet.
In another aspect of this invention, the composition of coating and particle is obtained by the reaction of colloidal sol and catalyzer, and wherein said colloidal sol comprises organoalkoxysilane or organotrialkoxysilane, poly-(silicone), hydrophilic additive and makes the biological catalyst of hydrated carbon dioxide.
Relate to a kind of for certainly containing CO on the other hand 2gas remove CO 2method, described method comprises to be made containing catalysis CO 2the liquid of the immobilized enzyme of hydration or the suspension of immobilized enzyme particle with containing CO 2gas contact to promote CO on commercial contact device 2diffuse in described liquid, CO subsequently 2change into hydrogen ion and bicarbonate ion.
Relate to a kind of for certainly containing CO on the other hand 2gas remove CO 2method, described method comprise makes liquid with containing CO 2gas contact to promote CO 2diffuse in described liquid, and make the CO in described liquid 2with the carrier contact of coating as herein described with catalysis CO 2hydration and formed and comprise the liquid of the process of hydrogen ion and bicarbonate ion.
Another aspect of the present invention relates to a kind of immobilized enzyme comprising enzyme and immobilization material, wherein said enzyme is embedded in described immobilization material and described immobilization material is obtained by the reaction of colloidal sol and catalyzer, and described colloidal sol comprises organoalkoxysilane or organotrialkoxysilane or metasilicic acid ester, (poly-(silicone)) and enzyme.
Relate to a kind of method for the preparation of porous granule as herein described on the other hand, it comprises mixed oxyalkyl silane or metasilicic acid ester and/or organotrialkoxysilane, gathers (silicone), hydrophilic additive, carbonic anhydrase, catalysts and solvents with the porous granule of the enzyme of formation containing embedding.
Relate to a kind of method of the carrier for the preparation of coating as herein described on the other hand, it comprises mixed oxyalkyl silane and/or organotrialkoxysilane, gathers (silicone), hydrophilic additive, carbonic anhydrase and solvent to form colloidal sol, make described colloidal sol and catalyst exposure to form gel, and make solid carrier and described gel contacts.
Relate to a kind of carrier of coating on the other hand, it comprises solid carrier and cambial application composition on the surface of described solid carrier, and wherein said application composition comprises immobilized enzyme as herein described.
Other target and feature will partly show hereinafter and easily know and partly point out.
Invention describes
Find to utilize sol-gel process immobilized enzyme in polysilicates/polysiloxane source property material can produce the CO showing and make in water 2change into the functional material that the ability of bicarbonate radical and proton is outstanding.These materials can be used as coating deposition and use on solid-state carrier or with suspended particles form.These materials are provided for the remarkable benefit related in the industrial application of enzyme catalyst.
Polysilicates as herein described-silicone copolymeric material provides a kind of multifunctional platform for immobilized enzyme.This multifunctionality partly can be higher based on the degree selecting component substituting group to be improved owing to the character of particle and coating.For example, the hole dimension of coating, hydrophilic/hydrophobic, transport properties and enzyme are functional by suitably selecting component substituting group to be controlled.
Polysilicates as herein described-silicone copolymer coating can be applicable to solid carrier.What advantageously polysilicates-silicone copolymer coating can be applicable to commercially available acquisition is applicable to various reactor, comprises the packing material in packed bed reactor.
The carrier of coating can comprise the polysilicates-silicone multipolymer of immobilized biocatalyst, and described polysilicates-silicone multipolymer is adhered to solid carrier by coating of adhering.
These materials also can be used for applying the solids that can be used in packed bed or fluidized-bed reactor.
Or these methods as herein described also can be used for producing the particle of the granularity with homogeneous or distribution, and be commonly called xerogel, it can be used in fluidized-bed reactor or tower contactor.
Gained polysilicates/polysiloxane copolymer source property xerogel is the porous particle of granularity of display certain limit, and with to allow highly to retain immobilized enzyme similar with the coating of its catalytic activity.
Chemistry and the physical properties of granularity, hole dimension and characteristic are controlled by synthetic method.
Material as herein described can be polysilicates/polysiloxane copolymer as described in more detail below.
For example, compared to exposed pottery and stainless steel packing material, greatly add with the packing material of the immobilized enzyme coating prepared according to method as herein described the speed that carbon dioxide conversion becomes bicarbonate radical.For example, at 45 DEG C, continued to be greater than 200 days in continuous flow reactor, reached lasting CO at a high speed 2transform.
Equally, produced sample and be continued above 1 year and tested and find that described sample still retains the catalytic activity exceeding blank solvent.
The carrier of coating as herein described, method and system are specially adapted to the carbonic acid gas in trapping and fluid partitioning environment.
In addition, coating as herein described carrier, method and system can be specific for trapping and isolating the carbonic acid gas in aqueous environments.
The carrier of coating
The carrier of coating as herein described comprises solid carrier, cambial application composition on the surface of described solid carrier, and described application composition comprises polysilicates-silicone multipolymer and hydrophilic additive and/or tensio-active agent in some cases; And be embedded in the biological catalyst of the catalysis hydrated carbon dioxide in described application composition.They are applicable in biological industry method.
Because biological catalyst catalysis hydrated carbon dioxide, so the carrier of coating is specially adapted in the method for trapping and carbon dioxide sequestration.Specifically, the biological catalyst of catalysis hydrated carbon dioxide comprises carbonic anhydrase.
Usually, the carrier of coating comprises the enzyme be fixed in application composition, and wherein said application composition forms one or more layer on the surface of solid carrier.
Application composition can use sol-gel process to prepare, wherein colloidal sol and catalyzer reaction under enzyme exists.Gained coating comprises polysilicates-silicone multipolymer, and wherein said enzyme is fixed in the hole of described polysilicates-silicone copolymer structure.
Solid carrier
The size of solid carrier, shape and the visual application-specific of surface characteristic and change.In many cases, solid carrier is conformed with it is desirable that there is relatively high surface-area to make can be used for the maximize with coating contacts.Depending on application-specific, preferred material should have heat and chemical stability with at pH7 to 11 and temperature 40 DEG C to 130 DEG C use.Preferred operations temperature range normally 40 DEG C to 60 DEG C.Stainless steel, polymkeric substance and stupalith such as have the heat and chemical feature that have and be used in many application.
Solid carrier can be the random of commercially available acquisition or structurizing packing material.The example of the random packing material of commercially available acquisition comprises Berl saddles (Berl saddle) filler, Intalox saddle (Intalox saddle) filler, Raschig ring (Raschig ring) or Pall ring (Pall ring) filler.Random packing material can comprise various material, comprises such as pottery, plastics, stainless steel and combination thereof.The example of the structurizing packing material of commercially available acquisition comprises ceramic integral material and structurizing steel and plastic filling material.These packing materials are specially adapted in packed bed reactor.
The packing material of commercially available acquisition is applicable, because they usually have high surface-to-volume ratio and immobilization material can be adhered to the surface of packing material, and therefore can efficient for industrial application.
When as described herein coating, business packing material is specially adapted to wherein in the industrial environment of gas phase capturing carbon dioxide.
The surface of solid carrier can be processed to provide desirable character before coating.For example, the surface of solid ceramic carrier is usually corroded to increase the number of usable surface sum reactive functional groups.Stainless steel carrier can stand scale removal or chemical oxidation for similar object.
The surface of solid carrier can before application of paint with primer coating pre-treatment to provide reactive part in the surface of carrier.This can provide the adhesion between carrier and coating to improve.Usually, base paint comprises the organic and/or inorganic polymer containing pendant hydroxyl group or silanol group functional group.
Coating
Because coating is used for immobilized enzyme, so it is called as immobilization material sometimes in this article.These coating as herein described or immobilization material are polysilicates-silicone multipolymers.
Polysilicates as herein described-silicone copolymer coating provides a kind of multifunctional platform for immobilized enzyme.This multifunctionality partly can be higher based on the degree selecting component substituting group to be improved owing to the character of coating.For example, the hole dimension of coating, hydrophilic/hydrophobic and enzyme are functional by suitably selecting component substituting group to be controlled.
The coating porousness that extensively can distribute between microporosity and macroporosity contributes to being transported in paradigmatic structure by reactant and product and transporting out paradigmatic structure.Therefore, enzyme can be effectively retained in coating the activity unduly limiting it by three dimensional matrix.
Xerogel particles
Xerogel particles as herein described comprises polysilicates-silicone multipolymer, hydrophilic additive and is embedded in the biological catalyst of the catalysis hydrated carbon dioxide in particle composition.The suspension of resulting materials is applicable in biological industry method.
Gained particle can use aqueous diluent or alcohol thinner to be synthesized in single pot.
Granularity is usually in the scope of hundreds of nanometer to hundreds of microns.Usually, for the granularity in suspension described herein application in the scope of 25 to 50 μm, 50 to 75 μm or 100 to 250 μm.
As above-mentioned coating, select synthetic method and reactive component to can be used for the character of hiding of Control granularity and matrix, comprise granularity, hole dimension and hydrophobicity.
Usually, optimization xerogel particles is made up of 2 to 10 % by weight immobilized enzyme.But enzyme weight percent can control easily through the adjustment enzyme amount be added in synthetic mixture.
The particle porosity that also extensively can distribute between microporosity and macroporosity is used for helping be transported in paradigmatic structure by reactant and product and transport out paradigmatic structure; This porousness of particle can reduce mass transfer limit.Therefore, enzyme is effectively retained in the activity significantly not reducing enzyme in coating by three dimensional matrix.
Usually, at room temperature pH about 10 times, in carbonate buffer solution, go through a couple of days, the view of time of several weeks and several months observes and be greater than 80% enzyme and retain.
The enzymic activity of these particles is shown in batch reactor container and in counter-current tower.
In batch reactor research, the suspension containing 0.2 % by weight particle in 2.0M salt of wormwood/saleratus (pH10.0) has shown mass transfer coefficient (K g) up to 0.16mmol/sm 2kPa.
In batch reactor research, under the carbonic anhydrase be fixed in polysilicates/Silicone particles has been presented at similar load level, exceed strengthening the property of soluble enzyme.
This above-mentioned enhancing phenomenon is by the density owing to particle lower (namely void volume is higher) and they are lower in the concentration of the surface of reaction soln subsequently.This surface concn of immobilized enzyme particle reduces to be contributed to the mass transfer of liquid phase from gas phase.
Except batch reactor system, prepared comparatively large vol suspension and containing random packing and structuring filling as the flow through reactors of contactor material in analyze.The catalysis observed in the circulation suspension system of good distribution improves up to six in packed bed reactor system times.
Polymeric stickers is used to make xerogel particles be connected to solid carrier
As a kind of alternative method utilizing above-mentioned xerogel particles, polymeric stickers can be used for the surface making to be adhered to solid carrier containing enzyme powder.
The typical polymers tackiness agent that can be used in this method is epoxide, carbamate, resin, cyanoacrylate and methacrylic ester.Usually, epoxide and carbamate are preferred.
Solid carrier is by being impregnated in polymeric stickers the polymeric stickers process being used in and being suitable for diluting in the solvent of selected polymeric stickers by solid carrier.Before polymeric stickers solidifies completely, polymeric stickers layer is contacted with the polysilicates-silicone copolymer powder particle comprising enzyme.The solid carrier of at room temperature dry gained coating 3 hours, and then thermofixation 24 to 96 hours at 55 DEG C to 90 DEG C.
Usually, by then using the solid carrier of polymeric stickers coating to contact with two-component epoxy or urethane polymer tackiness agent process solid carrier with the polysilicates-silicone copolymer powder particle comprising enzyme in the polymeric stickers that solid carrier be impregnated in not exclusively solidification.Again, the solid carrier of at room temperature dry gained coating 3 hours, and then thermofixation 24 to 96 hours at 55 DEG C to 100 DEG C.
Gains are structuring fillings of the polysilicates-silicone multipolymer immobilized enzyme particle coating with adhesion.
In addition, the method of carrier for the preparation of coating can comprise mixing (i) organoalkoxysilane or organotrialkoxysilane or metasilicic acid ester, (ii) poly-(silicone), (iii) hydrophilic additive, (iv) carbonic anhydrase, and (v) solvent is to form colloidal sol; Make described colloidal sol and catalyst exposure to form gel; Dry described gel and form xerogel particles; Make solid carrier and adhesion coating contacts; And make the described solid carrier with described adhesion coating contact to be formed the carrier of described coating with described xerogel particles.
The structurizing packing material applied by this method has shown mass transfer coefficient (K g) up to 0.12mmol/sm 2kPa.
polysilicates-silicone multipolymer
The composition of coating as herein described and particle comprises polysilicates-silicone multipolymer, and it is obtained with poly-(silicone) by organoalkoxysilane or organotrialkoxysilane usually.Because silicon ester and silicone can be designed to be easy to form Space network of polymer in the solution, so they can be used for forming the polymkeric substance for Encapsulated Enzyme.
Polysilicates-silicone multipolymer can be obtained by the reaction of colloidal sol and catalyzer, described colloidal sol comprises (i) organoalkoxysilane or organotrialkoxysilane, (ii) poly-(silicone), (iii) hydrophilic additive, and the biological catalyst of (iv) catalysis hydrated carbon dioxide.Colloidal sol optionally comprises tensio-active agent further.
As described in more detail below, the biological catalyst of catalysis hydrated carbon dioxide can be carbonic anhydrase.
Organoalkoxysilane can have formula 1 structure
Wherein R 1, R 2, R 3and R 4hydrogen or C independently 1-C 4alkyl; R 1, R 2, R 3and R 4preferably methyl or ethyl independently.
Organoalkoxysilane generally includes tetramethylorthosilicate, tetraethylorthosilicise, methyl triethyl ortho-silicate, ethyl-trimethyl ortho-silicate, dimethyl diethyl ortho-silicate, silicic acid four glyceryl ester, Starso or its combination.Tetramethylorthosilicate and tetraethylorthosilicise are especially preferred.
Organotrialkoxysilane has formula 2 structure
Wherein R 21, R 22, R 23and R 24hydrogen or C independently 1-C 4alkyl; R 21, R 22, R 23and R 24preferably methyl or ethyl independently.
Organotrialkoxysilane is trimethoxymethylsila,e, trimethoxy ethylsilane or its combination normally.
Wetting ability organotrialkoxysilane also can be used for improveing moist and water-based transhipment.Preferred form comprises 2 [(methoxyl group (polyethyleneoxy) propyl group] Trimethoxy silane.
Poly-(silicone) is selected from the group be made up of poly-(siloxanes), poly-(silicic acid glyceryl ester) and polysilsesquioxane usually.
Preferably, poly-(silicone) material normally silanol or alkoxysilane-terminated.
Poly-(siloxanes) is poly-(silicone) of preferred type.Usually, poly-(siloxanes) has formula 3 structure
Wherein R 31, R 32, R 33and R 34hydrogen or C independently 1-C 4alkyl; R 31, R 32, R 33and R 34preferably methyl or ethyl independently.
Poly-(siloxanes) generally includes poly-(dimethyl siloxane), poly-(dimethyl siloxane)-altogether-poly-(oxyalkylene), gathers the segmented copolymer of (dimethyl siloxane)-g-poly-(oxyethane) and poly-(dimethyl siloxane) and poly-(oxyethane) or its combination.Preferably, poly-(siloxanes) is silanol stopped.Silanol stopped poly-(dimethyl siloxane) is preferably poly-(siloxanes).
The molecular-weight average of silanol stopped poly-(dimethyl siloxane) can be about 200 dalton (dalton), about 550 dalton, about 1100 dalton, about 2750 dalton or about 4200 dalton.Molecular-weight average can about 200 dalton to about 2750 dalton, about 200 dalton in about 1100 dalton or about 450 dalton to about 650 daltonian scopes.
The ratio of organoalkoxysilane or organotrialkoxysilane and poly-(silicone) is the parameter affecting enzymic activity.For example, increasing poly-(silicone) amount in sol solution relative to organoalkoxysilane or organotrialkoxysilane makes hole dimension and volume increase usually.There is the porous coating suitably controlled more be permeable in reactant flow, and allow enzymic activity to be able to higher level reservation subsequently.
In addition, use in carbon trapping system, hydrophobic components can be used, as alkyl silane (such as trimethoxymethylsila,e, trimethoxy (propyl group) silane, trimethoxy (butyl) silane and trimethoxy (octyl group) silane), but consumption should provide and has acceptable hydrophobic polysilicates-silicone multipolymer.
In some cases, the hydrophobicity of polysilicates-silicone copolymer coating or immobilization material can prevent the aqueous solution of reactant (such as carbonic acid gas) from contacting with enzyme, thus causes enzymic activity significantly to reduce.Sometimes, when hydrophobicity is too high, reactant may be too low for most highly effective reaction for reaching by the flow (especially when the carrier applied is used in aqueous environments) of coating or immobilization material.
When using the mixture of organoalkoxysilane and poly-(silicone), the mol ratio of organoalkoxysilane and poly-(silicone) normally about 1: 1, about 2: 1, about 3: 1, about 4: 1, about 5: 1, about 6: 1, about 7: 1, about 8: 1, about 10: 1, about 12: 1, about 15: 1 or about 20: 1.Mol ratio can about 1: 1 to about 20: 1, about 2: 1 to about 8: 1 or about 3: 1 to about 5: 1 scope in.
In addition, when using the mixture of organoalkoxysilane and poly-(siloxanes), the mol ratio of organoalkoxysilane and poly-(siloxanes) normally about 1: 1, about 2: 1, about 3: 1, about 4: 1, about 5: 1, about 6: 1, about 7: 1, about 8: 1, about 10: 1, about 12: 1, about 15: 1 or about 20: 1.Mol ratio can about 1: 1 to about 20: 1, about 2: 1 to about 8: 1 or about 3: 1 to about 5: 1 scope in.
hydrophilic additive
Colloidal sol for the preparation of coating and particle also can contain hydrophilic additive.
If prepared not existing under hydrophilic additive, polysilicates so as herein described-silicone copolymer coating has more hydrophobicity.This can be some application and accepted, particularly for the application in nonaqueous environment.But in other applications, high hydrophobicity can cause enzymic activity significantly to reduce.Therefore, desirable is mix in coating composition by hydrophilic additive, particularly when enzyme is used in aqueous environments during catalysis wetting ability reactant.
The example of Exemplary hydrophilic additive comprises poly-(vinyl alcohol), poly-(oxyethane), quaternary ammonium polymer, crown ether, cyclodextrin, tensio-active agent, poly-(1-methyl-4-vinylpridine bromide), poly-(acrylamide-methacryloyl oxygen base ethyMmethylammonium bromide) and combination thereof.
The quaternary ammonium polymer be applicable to can comprise such as poly-(diallyldimethylammonium chloride), poly-(1-methyl-4-vinylpridine bromide), poly-(acrylamide-methacryloyl oxygen base ethyMmethylammonium bromide) or its combination.Preferably, quaternary ammonium polymer comprises poly-(diallyldimethylammonium chloride).
Cyclodextrin additive can comprise such as alpha-cylodextrin, beta-cyclodextrin, γ-cyclodextrin and combination thereof.Beta-cyclodextrin is preferred.
Crown ether is the hydrophilic additive of preferred classes.The crown ether be applicable to comprises 12-crown-4,1,7-diaza-12-crown-4,1,4,8, the 11-tetra-thia ring tetradecane, 1,4,8,12-tetraazacyclododecane pentadecane, 15-hat-5,18-hat-6, dibenzo-18 crown-6, two hexamethylenes are-18-hat-6, (18-hat-6)-2,3 also, 11,12-tetracarboxylic acid, 1-azepine-18-hat-6, diaza-18-are preced with-6 and combination.The crown ether comprising 18-hat-6 is especially preferred.
Preferably, coating and particle are obtained by the colloidal sol comprising tetramethylorthosilicate, polydimethylsiloxane, crown ether and carbonic anhydrase.
tensio-active agent
Colloidal sol for the preparation of coating and particle also can contain tensio-active agent.
Tensio-active agent can serve as the flowing agent in coating and particle preparation.In addition, it can be used for the gained character controlling coating and particle; Comprise granularity, pore structure and size and wetting properties.
Be suitable for the tensio-active agent making additive and comprise N, two (3-D-glucose cocamidopropyl) the courage acid amides (BigCHAP) of N-, N, two (the 3-D-glucose cocamidopropyl) deoxycholamide (deoxidation BigCHAP) of N-, Volpo S 10 (BRIJ35 and BRIJ58P), 2-cyclohexyl methyl-β-D-Maltose glycosides (CYMAL-1), 2-cyclohexyl-ethyl-β-D-Maltose glycosides (CYMAL-2), cyclohexylpentyl-β-D-Maltose glycosides (CYMAL-5), cyclohexylhexyl-β-D-Maltose glycosides (CYMAL-6), decyl-β-D-pyrans maltoside, positive dodecyl-β-D-Maltose glycosides, positive hexadecyl-β-D-Maltose glycosides, undecyl-β-D-Maltose glycosides, decyl-β-D-1-thio-pyrylium maltoside, octyl group-β-D-thioglucopyranoside, digitonin, dimethyldecylphosphine oxide, dodecyl dimethyl phosphine, (Octylphenoxy) polyethoxyethanols ( cA630), N-capryloyl-N-METHYL-ALPHA-L-GLUCOSAMINE (MEGA-8), N-nonanoyl-N-METHYL-ALPHA-L-GLUCOSAMINE (MEGA-9), N-decanoyl-N-METHYL-ALPHA-L-GLUCOSAMINE (MEGA-10), polyoxethylene octylphenyl phenol ( p40 surrogate), polyox-yethylene-polyoxypropylene block copolymer ( f-68), PEG-block-poly-(propylene glycol)-block-PEG ( p-123) saponin, SPE-103 ( ), polyoxethylene octylphenyl phenol (such as x-100 and x-114), the polyoxyethylene deriv of Span 20 (such as 20, 40 Hes 80), N, N-dimethyl amino dodecane-N-oxide compound, cetyl trimethylammonium bromide (CTAB), alcohol ethoxylate ( a7) and combination.
Preferred surfactant materials is cetyl trimethylammonium bromide.The polyoxyethylene deriv of Span 20 is also preferred.
the carrier of the coating obtained by sol gel reaction
Coating can be obtained by the reaction of colloidal sol and catalyzer.Usually, colloidal sol comprises poly-(silicone) and organoalkoxysilane and/or organotrialkoxysilane and the enzyme throughout aqueous medium dispersion.Introduce catalyzer to assist polyreaction, wherein organoalkoxysilane and/or organotrialkoxysilane and poly-(silicone) stand to be hydrolyzed and with after condensation, to be incorporated in gel-like material by enzyme thus.Gel is coated on solid carrier, and described solid carrier then stands thermofixation.Gains are three-dimensional network polymer, and wherein enzyme molecule is fixed in the hole of paradigmatic structure.
According to the coating that this method produces, there is favourable character usually.For example, paradigmatic structure can play a part to make enzyme stablize heat resistanceheat resistant and chemical depletion, has simultaneously and is enough to make immobilized enzyme retain the hole dimension of the catalytic activity of its signal portion.
Catalyzer can comprise Neutral ammonium fluoride, Sodium Fluoride, tetrabutylammonium fluoride, ammonium hydroxide, sodium hydroxide, potassium hydroxide, sodium hydroxide or its combination.The catalyzer comprising Neutral ammonium fluoride is preferred.
More generally, catalyzer can comprise acid or alkali, comprises Lewis acid and Lewis base.Catalyzer can be used for the hydrolysis or the condensation that cause acid or alkali induction.
multiple coating
Solid carrier also can with two-layer or more coating coating.Extra play for increasing the total thickness of coating, and increases the enzyme amount that can be loaded on solid carrier thus.If there is two-layer or more layer, so preferably each layer comprises the enzyme of embedding.
the physical properties of coating
Usually, the surface-area of coating is at least about 1m 2/ g, at least 10m 2/ g, at least about 20m 2/ g, at least about 30m 2/ g, at least about 40m 2/ g, at least about 50m 2/ g, at least about 60m 2/ g, at least about 70m 2/ g, at least about 80m 2/ g, at least about 90m 2/ g, at least about 100m 2/ g, at least about 150m 2/ g, at least about 200m 2/ g or at least about 300m 2/ g.
The surface-area of coating is usually at about 1m 2/ g to about 400m 2/ g, about 5m 2/ g to about 300m 2/ g, about 10 are to about 150m 2/ g or about 15 is to about 100m 2in the scope of/g.
The bore dia of coating is generally about 1nm to about 200nm, more preferably from about 2nm to about 80nm, more preferably from about 20nm to about 80nm.
The total pore volume of coating is generally at least about 3 μ L/g to 500 μ L/g.Usually, at least about 20%, at least about 30%, at least about 40%, at least about 50%, at least about 60%, at least about 70% or be attributable to bore dia in about 20nm and the hole about between 80nm at least about the total pore volume of 80%.
Polysilicates-silicone multipolymer can be used as immobilization material.In that case, immobilized enzyme comprises enzyme and immobilization material.Enzyme is embedded in immobilization material and immobilization material is obtained by the reaction of colloidal sol and catalyzer, described colloidal sol comprises (i) organoalkoxysilane or organotrialkoxysilane, (ii) poly-(silicone), and (iii) enzyme.Described above is colloidal sol, organoalkoxysilane or organotrialkoxysilane and poly-(silicone).
In addition, enzyme is embedded in immobilization material and immobilization material is obtained by the reaction of colloidal sol and catalyzer, described colloidal sol comprises (i) organoalkoxysilane or organotrialkoxysilane, and (ii) gathers (siloxanes), and (iii) enzyme.Described above is colloidal sol, organoalkoxysilane or organotrialkoxysilane and poly-(siloxanes).
Biological catalyst and enzyme
Coating also comprises the catalyzer of catalysis hydrated carbon dioxide.Usually, catalyzer can be biological catalyst, as enzyme, ribozyme, ribodesose enzyme, enzyme mimics or can the organic or inorganic compound of catalysis hydrated carbon dioxide.
Preferably, biological catalyst is carbonic anhydrase.Not bound by theory, it is believed that carbonic anhydrase passes through in avtive spot, have the zinc atom with three histidine side chains coordinations, there is the zinc atom four-coordination position occupied by water simultaneously and carry out catalysis hydrated carbon dioxide.Water can cause hydrogen-oxygen bond polarization by zinc atom coordination.4th Histidine accepts the proton from the water molecules of coordination, thus produces the oxyhydroxide being connected to zinc atom.Carbonic anhydrase activity site is also containing for the pocket of carbonic acid gas, and described pocket makes carbonic acid gas near hydroxide radicals and the oxyhydroxide making to be rich in electronics attacks carbonic acid gas to form bicarbonate radical.In this way, carbonic anhydrase is involved in hydrated carbon dioxide.(Tripp, B.C., Smith, and Ferry K., J.G. (2001) .Carbonic Anhydrase:New Insights for an Ancient Enzyme.Journal of Biological Chemistry, 276 (52), 48615-48618.)
Usually, enzyme is embedded in the hole of three-dimensional polysilicates-silicone copolymer networks.
When coating or immobilized enzyme contain enzyme, the naturally occurring enzyme of naturally occurring enzyme, synthetic enzyme, artificial enzyme and modification can be utilized.In addition, can use by the through engineering approaches enzyme of natural or orthogenesis through engineering approaches in addition.In addition, the organic or inorganic molecule of the character of analogue enztme can be used.
Enzyme can comprise lipase, glucose isomerase, nitrilase, glucose oxidase, proteolytic enzyme, carbonic anhydrase, stomach en-, amylase, fungal amylase, maltogenic amylase, cellulase, Sumylact L, esterase, carbohydrase, hemicellulase, pentosanase, zytase, Starch debranching enzyme, beta-glucanase, acetolactate decarboxylase, beta-glucosidase, L-Glutamine deaminase, penicillin acylase, chloroperoxidase, aspartic acid β-decarboxylase, Maltose 4-glucosyltransferase, subtilisin, amino acylase, alcoholdehydrogenase, amino-acid oxidase, phospholipase, urase, Sterol esterase, desulfinase, lignin peroxidase, polygalacturonase, oxydo-reductase, dextranase, glucuroide, tilactase, glucoamylase, maltin, sucrase, saccharase, naringinase (naringanase), bromeline (bromelain), ficin (ficin), papoid (papain), stomach en-, peptase, rennin, thermolysin (thermolysin), trypsinase, triglyceride level enzyme, stomach proesterase, Phosphoric acid esterase, phytase, Ntn hydrolase, L-Glutamine deaminase, N,O-Diacetylmuramidase, katalaze enzyme, desaturase, peroxidase, lyase, FURAMIC ACID, histidase, transaminase, ligase enzyme, cyclase, racemase, mutase, oxydase, reductase enzyme, lignoenzyme, laccase, chloroperoxidase, haloperoxidase, hydrogenase, nitrogenase, oxynitrilase or its combination.
Preferably, biological catalyst or the enzyme of fixing catalysis hydrated carbon dioxide are carbonic anhydrases.Bicarbonate radical and proton is changed into for carbonic anhydrase (CA) the catalysis carbonic acid gas in system described herein and water reversible.CA represent a family in configuration aspects and at the various enzyme of genetic aspect, described enzyme produces (Tripp by different precursor independently due to convergent evolution, B.C., Smith, and Ferry K., J.G. (2001) .Carbonic Anhydrase:New Insights for an Ancient Enzyme.Journal of Biological Chemistry, 276 (52), 48615-48618; Elluche, S. and s. (2010) .Carbonic Anhydrases in Fungi.Microbiology, 156,23-29).Various CA enzyme cannot not be grouped into totally DNA sequence dna similarity and five irrelevant structured sorts (such as α, β, γ, δ and ε) different in protein structure with avtive spot structure.Although these structures there are differences, but the avtive spot of the CA enzyme of all categories all to work (Tripp together with the necessary single divalent metal cofactors of catalysis, B.C., Smith, and Ferry K., J.G. (2001) .Carbonic Anhydrase:New Insights for an Ancient Enzyme.Journal of Biological Chemistry, 276 (52), 48615-48618).Most common metal cofactor in CA enzyme is zinc.
The CA of α classification is the principal mode of expressing in Mammals, and is the most fully characterized in all CA classifications.There are at least 16 kinds of α-CA or CA relevant enzyme (Supuran that find in animal, C.T. (2008) .Carbonic Anhydrases-An Overview.Current Pharmaceutical Design, 14,603-614) and 6 kinds of forms finding in bacterium.The CA of β classification sees (Zimmerman in green plants, blue-green algae and bacterium, and Ferry S.A., J.G. (2008) .The β and γ Classes of Carbonic Anhydrases.Current Pharmaceutical Design, 14,716-721) (Rowlett, R.S. (2010) .Structure and Catalytic Mechanism of the β-Carbonic Anhydrases.Biochimica et Biophysica Acta, 1804,362-373).γ classification sees in bacterium and an example will for from thermophilic sarcina methanica (Methanosarcina thermophila, CAM) CA (Zimmerman, and Ferry S.A., J.G. (2008) .The β and γ Classes of Carbonic Anhydrases.Current Pharmaceutical Design, 14,716-721).CAM gene to be cloned in intestinal bacteria and to express (Alber containing Zn form, and Ferry B.E., J.G. (1996) .Characterization of Heterologously Produced Carbonic Anhydrase from Methanosarcina thermophila.Journal of Bacteriology (June), 3270-3274), but it in Fe, Cd or Co form time have more activity.δ classification is found in (Zimmerman in marine diatom Wei Shi hailian seaweed (Thalassiosira weissflogii), and Ferry S.A., J.G. (2008) .The β and γ Classes of Carbonic Anhydrases.Current Pharmaceutical Design, 14,716-721).This example protein is a kind of dimer, and wherein monomer molecule amount is 27kD.Described protein will in conjunction with Zn-, but Fe-and/or Cd-preponderates in vivo.Equally, ζ classification also sees (Zimmerman, S.A. and Ferry, J.G. (2008) .The β and γ Classes of Carbonic Anhydrases.Current Pharmaceutical Design in marine diatom Wei Shi hailian seaweed, 14,716-721).The dimer of described protein to be also a kind of molecular weight be 50-60kD.The catalytic property of these two classifications is not yet characterized.
Depending on tissue or cellular compartment position (such as cytosol, plastosome, secretion and film associate), Mammals CA enzyme is divided into four extensive subgroups.CAII and CAIV enzyme is most catalytic efficiency in all CA characterized, and display catalytic rate is close to the theoretical limit of diffusion control speed.CA IV shows extra high temperature stability, it is believed that this exists caused by two disulfide linkage by enzyme.
Use Mammals carbonic anhydrase, plant carbonic anhydrase or microorganism carbonic anhydrase; Preferred BCA II or people's carbonic anhydrase IV.People's carbonic anhydrase IV can obtain from the William S.Sly of Saint Louis University (St.Louis University) and be described in more detail in below with reference in document: T.Okuyama, S Sato, X.L.Zhu, A.Waheed and W.S.Sly, Human carbonic anhydrase IV:cDNA cloning, sequence comparison, and expression in COS cell membranes, Proc.Natl.Acad.Sci.USA 1992, 89 (4), 1315-1319 and T.Stams, S.K.Nair, T.Okuyama, A.Waheed, W.S.Sly, D.W.Christianson, Crystal structure of the secretory form of membrane-associated human carbonic anhydrase IV at resolution, Proc.Natl.Acad.Sci.USA1996,93,13589-13594.
Also the compound of the avtive spot of simulation carbonic anhydrase can be used.For example, various metal complex is for simulating carbonic anhydrase activity site.Such as [Zn 2(3,6,9,12,20,23,26,29-eight aza-tricycle [29.3.1.1 14,18] hexatriacontane-1 (34), 14,16,18 (36), 31 (35), 32-six alkene) (CO 3)] Br 27H 2o and [Zn 2(3,6,9,12,20,23,26,29-eight aza-tricycle [29.3.1.1 14,1 8] hexatriacontane-1 (34), 14,16,18 (36), 31 (35), 32-six alkene) (CO 3)] Br 20.5CH 3cOCH 35H 2o (see Qi etc., Inorganic Chemistry Communications2008,11,929-934).That be also used as the stand-in of carbonic anhydrase is [three (2-benzoglyoxaline ylmethyl) amine Zn (OH) 2] 2+, [three (2-benzimidazolyl-) amine Zn (OH) 2] (ClO 4) 2[three (hydroxyl-2-benzoglyoxaline ylmethyl) amine Zn (OH)] ClO 41.5H 2o is also for hydration CO 2.(see Nakata etc., The Chemistry Letters, 1997,991-992 and Echizen etc., Journal of In organic Biochemistry2004,98,1347-1360).
Preferably, enzyme is carbonic anhydrase; More preferably, carbonic anhydrase is alpha-carbon acid anhydrides enzyme, β-carbonic anhydrase, γ-carbonic anhydrase, δ-carbonic anhydrase or ε-carbonic anhydrase.Carbonic anhydrase is alpha-carbon acid anhydrides enzyme and is the carbonic anhydrase that kytoplasm carbonic anhydrase, plastosome carbonic anhydrase, the carbonic anhydrase of secretion or film are relevant further.
More preferably, carbonic anhydrase is Mammals carbonic anhydrase, plant carbonic anhydrase or microorganism carbonic anhydrase; Most preferably, be microorganism carbonic anhydrase.
the stabilization of enzyme and immobilization
For purposes of the present invention, if loss of activity speed is less than the loss of activity speed of seen on-fixed enzyme under the same conditions, so enzyme is " stable ".Enzyme immobilizatio provides the significant advantage of stability aspect.Enzymic activity is measured by the means of the product generation of display enzyme mediation.Follow the trail of activity by chemoluminescence, electrochemistry, mass spectroscopy, spectrophotometric (i.e. UV-Vis), radiological chemistry or fluorometric assay, wherein measure properties strength at initial time, and then the time length of experiment is monitored.
When the chemical conversion of enzyme continuous catalysis, enzyme can retain it at least about 10%, 20%, 30%, 40%, 50% or more initial activity.
With regard to the stabilization of enzyme, coating and particle (i.e. enzyme immobilization material) provide chemistry and/or mechanical barrier prevent or hinder enzyme denaturation.For this reason, it is believed that enzyme immobilization material retrains enzyme for physically, thus prevent enzyme from launching.The process that the three-dimensional structure of enzyme autofolding is launched is a kind of enzyme denaturation mechanism.
When active catalytic chemical conversion described above, the enzyme with comparatively high temps or pH stability also can retain the lasting at least about 10 days at least about the initial catalytic activity of 75% of it.
Enzyme is fixed by immobilization material, and now the enzyme of at least 50%, 60%, 70%, 80% or more to be retained in polysilicates-silicone copolymer particle at least 5,10,20,40,60,80,100,150,200,250,300,350 days or more.In addition, enzyme retains 5-365,10-365,20-365,40-365,60-365,80-365,100-365,150-365,200-365,250-365,300-365 or 350-365 days by immobilization material.
Preparation method
Usually, sol-gel process technology can be used to prepare the coating or the immobilization material that comprise the enzyme of embedding." sol-gel " method is that wherein colloidal compositions or " colloidal sol " serve as the method for the integrated network of network polymer and/or discrete particle or the precursor of " gel ".
Colloidal sol comprises organoalkoxysilane and/or organotrialkoxysilane and/or metasilicic acid ester, gathers (silicone) and dispersion enzyme in an aqueous medium.For producing jel product, initiated polymerization, wherein organoalkoxysilane and/or organotrialkoxysilane carry out condensation reaction with poly-(silicone) under enzyme exists.Catalyzer can be used for assisting polymerization process.
Described process causes forming network polymer, and wherein enzyme molecule is fixed in the hole of paradigmatic structure.One of favourable character of jel product is that immobilized enzyme makes enzyme be retained in the hole of immobilization material.
In addition, immobilized enzyme can retain the catalytic activity of the signal portion of described enzyme, as described in more detail in above enzyme stability chapters and sections.
Colloidal sol also can comprise hydrophilic additive, and it can be used for the character optimization making jel product.More than detail Exemplary hydrophilic additive.
Solid carrier
The size of solid carrier, shape and the visual application-specific of surface characteristic and change.Usually, preferred material should have the thermostability and chemical stability that are enough to stand potential harsh method condition.Stainless steel and stupalith such as have for the favourable heat of many application and chemical feature.The foregoing describe type and their the physics and chemistry character of solid carrier.
Solid carrier optionally stood corrosion step before applying it with colloidal compositions.An advantage of corrosion step is its number for increasing the functional group on surface-area and carrier, and this contributes to carrying out more effective coating method.
Usually, corrosion reagent comprises acid.Hydrogen fluoride is preferred acid, and is particularly preferred when solid carrier comprises stupalith.
Corrosion reagent can comprise oxygenant.Preferred oxygenant comprises hydrogen peroxide, ammonium hydroxide and composition thereof.The mass ratio of the mixture of hydrogen peroxide and ammonium hydroxide is generally about 1: 4 to about 4: 1, is more typically the ratio of about 1: 1.
In some cases, corrosion step will comprise makes solid carrier contact with reductive agent, makes solid carrier and oxidising agent subsequently.
In the case of stainless steel, the process as washing, polishing, scale removal and sandblasting can be used for pretreating surface.Typical case's detergent solution can comprise hydrofluoric acid and/or nitre aqueous acid.
Carrier also can use primer coating pre-treatment.Usually, base paint comprises the organic and/or inorganic polymer containing pendant hydroxyl group or silanol-functional base.The number of the functional moiety of the surface of carrier can be increased in primer coating pre-treatment.This can be used for the adhesion between carrier and coating, and this measure can provide the advantage of the overall coating method that is above standard.
The selection of primer coating is depended on to the certain material forming carrier surface.For example, ceramic monolith and stainless steel carrier all can with tetramethoxy-silicane or tetraethoxysilane process under the existence of acid or alkaline catalysts.Primer coating can then in addition thermofixation, thus produces the silicon ester coating that reactive silicon triacontanol group covers the surface of carrier.
When coating is obtained by the reaction of colloidal sol and catalyzer, and colloidal sol is when comprising organoalkoxysilane or organotrialkoxysilane and poly-(silicone), the functional moiety being exposed to the surface of carrier can allow to connect the gained polysilicates-silicone multipolymer as coating.
The component of colloidal compositions (" colloidal sol ")
Colloidal compositions or " colloidal sol " comprise organoalkoxysilane and/or organotrialkoxysilane, gather (silicone) and enzyme.
Colloidal sol also can comprise hydrophilic additive, and it can be used for the character optimization making jel product.
Colloidal sol also can comprise tensio-active agent, and it can be used for the character optimization making jel product.
Colloidal sol also can comprise optional catalyst to assist polymerization process.
biological catalyst and enzyme
Colloidal sol comprises the biological catalyst of catalysis hydrated carbon dioxide.Biological catalyst become be embedded in the three-dimensional polysilicates-silicone copolymer networks formed according to above-mentioned sol-gel process hole in.Usually, biological catalyst is enzyme.
More than detail the enzyme being suitable for using together with this method.Also the compound of analogue enztme avtive spot can be used.
silicon ester and silicone
Colloidal sol comprises organoalkoxysilane and/or organotrialkoxysilane and gathers (silicone).More than detail and be applicable to typical silicon ester in this method and silicone.
As mentioned above, poly-(silicone) can be poly-(siloxanes).
Usually, the mol ratio of the organoalkoxysilane in colloidal sol and/or organotrialkoxysilane and poly-(silicone) is about 1: 1, about 2: 1, about 3: 1, about 4: 1, about 5: 1, about 6: 1, about 7: 1, about 8: 1, about 10: 1, about 12: 1, about 15: 1 or about 20: 1.Mol ratio can usually about 1: 1 to about 20: 1, about 2: 1 to about 8: 1 or about 3: 1 to about 5: 1 scope in.
In addition, the mol ratio of the organoalkoxysilane in colloidal sol and/or organotrialkoxysilane and poly-(siloxanes) is about 1: 1, about 2: 1, about 3: 1, about 4: 1, about 5: 1, about 6: 1, about 7: 1, about 8: 1, about 10: 1, about 12: 1, about 15: 1 or about 20: 1.Mol ratio can usually about 1: 1 to about 20: 1, about 2: 1 to about 8: 1 or about 3: 1 to about 5: 1 scope in.
hydrophilic additive
Sol solution optionally can comprise hydrophilic additive.Usually these additives are incorporated to the reservation of the wetting ability and increase enzymic activity that improve coating.More than detail the Exemplary hydrophilic additive be applicable in this method.
In a preferred embodiment, colloidal sol comprises tetramethylorthosilicate, polydimethylsiloxane and crown ether.
catalyzer
Catalyzer is comprised to assist polymerization process in colloidal sol.More particularly, catalyzer can be introduced in sol solution the polyreaction of assisting generation polysilicates-silicone multipolymer to comply with.Gains are three-dimensional polysilicates-silicone network copolymers, and wherein enzyme molecule is fixed in the hole of paradigmatic structure.
Catalyzer can comprise Neutral ammonium fluoride, Sodium Fluoride, ammonium hydroxide, sodium hydroxide or its combination.The catalyzer comprising Neutral ammonium fluoride is preferred.
Prepare colloid solution solution
According to method of the present invention, the colloidal solution comprising said components can be prepared.
Usually, preparation comprises the aqueous stock solution of enzyme separately, and mixes with the second preparation of the organic solution comprising silicon ester and silicone monomer and optional additives subsequently.
Enzyme normally preparation in buffered soln (such as phosphate buffered saline buffer), wherein the pH value of stoste can in the scope of about 6 to about 10.Usually, be preferred in about 6 and pH about between 8.
Enzyme is mixed with complete lytic enzyme with enough water, and does not increase required time of drying.Proenzyme liquid comprises the enzyme of about 50mg/mL, about 100mg/mL, about 150mg/mL, about 200mg/mL or about 300mg/mL usually.Enzyme concn in stoste is usually in about 50 scopes to about 200mg/mL.
If proenzyme liquid is preparation separately, so it should merge with the second preparation comprising organoalkoxysilane and/or organotrialkoxysilane and poly-(silicone) material and optional additive and mix until obtain emulsion or the homogenizing mixture of fine dispersion.Mixing is preferably carried out to higher shear power medium, and can use any common mixing device as known in the art to carry out.The limiting examples of possible mixing device comprises mechanical stirrer, static mixer, swivelling chute agitator, ultra-sonic generator and high pressure homogenisers.The part that mixing can be used as intermittent type, semibatch or continuation method is carried out.
The second solution comprising silicon ester and silicone monomer and optional additives pure (neat) can be prepared or prepare in dilute alcohol solution.Methyl alcohol or ethanol are the preferred alcohols for this object.
Some different methods can be used for merging the aqueous solution containing enzyme and the organic mixture containing monomer.These methods are included in that violent mixing is lower to be added in organic monomeric substance to enzyme aqueous solution or add enzyme aqueous solution in the mixture of the monomer of monomer or partial hydrolysis.Equally, the order of addition of catalyzer and thinner can be easy to change to obtain catalytic activity product.
The mol ratio of organoalkoxysilane and/or organotrialkoxysilane and hydrophilic additive normally about 48: 1, about 36: 1, about 24: 1, about 12: 1 or about 4: 1.Ratio can about 4: 1 to about 60: 1, about 15: 1 to about 45: 1 or about 30: 1 to about 40: 1 scope in.
The mol ratio of poly-(silicone) and hydrophilic additive normally about 12: 1, about 9: 1, about 6: 1, about 3: 1 or about 1: 1.Mol ratio can about 1: 1 to about 30: 1, about 2: 1 to about 20: 1, about 5: 1 to about 15: 1, about 6: 1 to about 12: 1 or about 8: 1 to about 10: 1 scope in.
In addition, the mol ratio of poly-(siloxanes) and hydrophilic additive normally about 28: 1, about 14: 1,12: 1, about 9: 1, about 7: 1, about 6: 1, about 3: 1 or about 1: 1.Mol ratio can about 1: 1 to about 30: 1, about 2: 1 to about 20: 1, about 3: 1 to about 20: 1, about 10: 1 to about 20: 1, about 5: 1 to about 15: 1, about 6: 1 to about 12: 1 or about 8: 1 to about 10: 1 scope in.
The mol ratio of organoalkoxysilane and/or organotrialkoxysilane and tensio-active agent normally about 130: 1, about 65: 1, about 32: 1, about 16: 1 or about 8: 1.Ratio can about 4: 1 to about 200: 1, about 40: 1 to about 80: 1 or about 50: 1 to about 70: 1 scope in.
The mol ratio of organoalkoxysilane and/or organotrialkoxysilane and carbonic anhydrase normally about 1300: 1.Ratio can in the scope of about 4000: 1 to about 600: 1.
The mol ratio of poly-(silicone) and carbonic anhydrase normally about 325: 1.Mol ratio can in the scope of about 1000: 1 to about 160: 1.
The mol ratio of poly-(siloxanes) and carbonic anhydrase normally about 325: 1.Mol ratio can in the scope of about 1000: 1 to about 160: 1.
Usually, the organoalkoxysilane in dilute alcohol solution and/or the amount of organotrialkoxysilane are at least about 10 % by weight, at least about 20 % by weight, at least about 30 % by weight, at least about 40 % by weight or at least about 50 % by weight.The amount of the organoalkoxysilane in dilute alcohol solution can in the scope of about 5 % by weight to about 50 % by weight, about 10 % by weight to about 40 % by weight or about 20 % by weight to about 30 % by weight.
Usually, the amount of poly-(silicone) in dilute alcohol solution is at least about 2.5 % by weight, at least about 5 % by weight, at least about 7.5 % by weight or at least about 12.5 % by weight.The mass percent of poly-(silicone) in dilute alcohol solution can in the scope of about 1 % by weight to about 20 % by weight, about 2.5 % by weight to about 15 % by weight, about 5 % by weight to about 12.5 % by weight or about 5 % by weight to about 7.5 % by weight.
In addition, the amount of poly-(siloxanes) in dilute alcohol solution is at least about 2.5 % by weight, at least about 5 % by weight, at least about 7.5 % by weight or at least about 12.5 % by weight.The mass percent of poly-(siloxanes) in dilute alcohol solution can about 1 % by weight to about 20 % by weight, about 2.5 % by weight to about 15 % by weight, about 5 % by weight to about 12.5 % by weight or about 5 % by weight to about 7.5 % by weight. scope in.
Colloid solution is applied on solid carrier
In another step of present method, solid-state carrier can apply with colloid solution solution.
State as discussed above, before coating step, usually solid-state carrier corroded or use primer coating process.
After preparing colloidal sol, by any ordinary method as known in the art, coating is put on solid carrier.For example, solid carrier applies by immersion coating, rotary coating, spray application, roll-type coating or submergence coating.Submergence coating, immersion coating or spray application are preferred method.Usually, solution is in medium in addition submergence coating to higher shear.Usually, spray application is carried out with heavy body low pressure atomizing rifle.
Solid carrier can use one deck, the coating of two-layer or more layer sol solution.Extra play for increasing the total thickness of coating, and increases the enzyme amount that can be loaded on solid carrier thus.
When utilizing additional coatings, usually make the solid carrier at room temperature drying about 15 to 30 minutes of coating.Then the carrier of coating is submerged in the container containing colloidal sol or with fog gun again and sprays again.Or, thermofixation can be applied between the coatings to promote surface adhering.
The carrier of dry coating
In another step of present method, the solid carrier of dry coating.
Usually, a part is dry is undertaken in the process of coating method.But, in most of the cases, after coating method completes, will extra time of drying be needed.Usually, coating is at room temperature dry.
Drying step relates to and removes aqueous phase and alcohol product haply completely from colloidal sol.When colloidal sol is dry, organoalkoxysilane, organotrialkoxysilane and poly-(silicone) unit stand polymerization, thus form network polymer gel gradually, and enzyme and hydrophilic additive become and be embedded in the hole of polymkeric substance simultaneously.
Gained coating retains its porousness usually.For example, the total pore volume of coating is generally at least about 3 μ L/g to 500 μ L/g.Usually have at least about 10m according to coating prepared by this method 2/ g, at least about 20m 2/ g, at least about 30m 2/ g, at least about 40m 2/ g, at least about 50m 2/ g, at least about 60m 2/ g, at least about 70m 2/ g, at least about 80m 2/ g, at least about 90m 2/ g or at least about 100m 2the surface-area of/g.
Thermofixation
Method for the preparation of immobilized enzyme can comprise mixing (i) organoalkoxysilane or organotrialkoxysilane or metasilicic acid ester, (ii) poly-(silicone), (iii) hydrophilic additive, (iv) carbonic anhydrase, and (v) solvent is to form colloidal sol; Make described colloidal sol and catalyst exposure to form gel; And described gel is solidified at the temperature of about 55 DEG C to about 85 DEG C.
Gel can solidify about 48 little of about 96 hours at the temperature of about 75 DEG C to about 100 DEG C.Gel can solidify about 48 little of about 96 hours at the temperature of about 80 DEG C to about 100 DEG C.Preferably, gel can solidify about 72 hours at about 85 DEG C.
When coating solid carrier, final composition can in addition thermofixation after coating and drying step complete.
Usually, the carrier of coating solidifies at temperature between about 35 DEG C and 110 DEG C.The solidification value of 55 DEG C to 85 DEG C is preferred.
Depending on the composition of solidification value, colloidal sol and the number of plies of coating, set time can in the scope of about 24 to about 96 hours.
Or, can utilize and rise to 75 DEG C gradually from 55 DEG C.At preferred method is included in 55 DEG C 24 hours, at 75 DEG C 72 hours subsequently.
Method for the preparation of immobilized enzyme can comprise mixing (i) organoalkoxysilane or organotrialkoxysilane or metasilicic acid ester, (ii) poly-(silicone), (iii) hydrophilic additive, (iv) carbonic anhydrase, and (v) solvent is to form colloidal sol; Make described colloidal sol and catalyst exposure to form gel; And described gel is solidified at the temperature of about 55 DEG C to about 100 DEG C.
Once solidification, gel can form the particle as described in following chapters and sections.
Particle suspension liquid is prepared from dry gel powder
As use soliquid coating solid-state carrier a kind of replacement scheme, suspension gelling can be made, then gel can dried, solidify and grind to form bulk powder.These powder are commonly referred to " xerogel ".Described powder also produces by spraying.
Usually, powder washing and hydration in such as carbonate and phosphatic conventional damping fluid.The pH of these damping fluids can in the scope of 7 to 10.Because most of active testing is at 0.8M/1.2M KHCO 3/ K 2cO 3carry out in solution (pH ≈ 10), so this provides a kind of in order to washing and the favourable damping fluid of hydration gained powder.
Powder can use mortar and pestle to improve hydration and particle distribution.
The sieve that powder also can be made to pass have different grain size cutoff value is to make narrow particle size distribution and improvement hydration.Usually, the sieve of cutoff value in the scope of < 500 μm, < 250 μm, < 125 μm and < 45 μm has been utilized.
Washing and hydration suitable amount time after, particle can be suspended in required solvent again.Usually, 0.8M/1.2M KHCO is used 3/ K 2cO 3solution (pH ≈ 10).
Usually, the suspension of the solids containing Different Weight per-cent can be prepared to trap CO 2.Required weight percent depends on the type of contactor used usually.The suspension of weight percent in the scope of 0.05 to 20 % by weight can be prepared.Usually, in batch reactor, be used in the suspension compared with low weight percentage in the scope of 0.05 to 10 % by weight.When these particles on packed bed reactor or dish contactor for circulation type system in time, higher weight percent solution can be needed reach required overall CO 2trapping.These weight percents can in the scope of 1 to 20 % by weight.
Once add particle in buffer solvent, namely multiple technologies can be used for distribution of particle and obtain the solution of good distribution.These technology comprise vibration, mechanically mixing, vortex, supersound process or its combination.
For removing the method and system of carbonic acid gas
The solid carrier of coating that wherein carbonic anhydrase is embedded in polysilicates-silicone multipolymer source property coating can be used for catalysis for from containing CO 2gas remove CO 2process.
Usually, method makes liquid under being included in the solid carrier existence of coating and contains CO 2gas contact to promote CO 2diffuse in described liquid and carry out catalysis CO 2hydration, forms the treated liquid comprising hydrogen ion and bicarbonate ion thus.Hydrogen ion also with the carbonate existed in solution from sub-combination, thus can form the second bicarbonate ion.
Described method also can comprise to be made liquid and contains CO 2gas contact; And the CO making in described liquid 2contact with above-mentioned immobilized enzyme with catalysis CO 2hydration and formed and comprise the treated liquid of hydrogen ion and bicarbonate ion.
Described method also can comprise to be made liquid and contains CO 2gas contact; And the CO making in described liquid 2contact with the particle of above-mentioned polysilicates-silicone multipolymer xerogel with catalysis CO 2hydration and formed and comprise the treated liquid of hydrogen ion and bicarbonate ion.
Usually, enzyme can catalysis as the hydration reaction of the first step of two steps orders:
CO 2+H 2O→H ++HCO 3 -(1)
CO 3 2-+H +→HCO 3 -(2)
By using carbonic anhydrase catalysis CO 2hydration [reaction (1)], CO 2the speed changing into bicarbonate form is accelerated.
This reaction is preferably less than 10.5 times generations at pH.The K of hydration reaction at 25 DEG C eq1.7 × 10 -3; Reaction at equilibrium is conducive to the CO of reaction formula 2/ H 2o side.In reaction (2), carbonate trapping reacts the proton produced in (1) and the motivating force produced in order to produce more bicarbonate radicals.
Carbonic anhydrase also can be used for catalysis bicarbonate radical and dewaters back and become CO 3 2-, CO 2and water.CO can be there is in carbonate to returning to be recycled to 2in the first reactor residing for dehydration.For example, NaHCO 3the chemical process of dehydration is as follows:
2NaHCO 3→Na 2CO 3+H 2O+CO 2(3)
After the heating, bicarbonate radical release CO 2the carbanion that can be recycled in hydration reaction is formed with water.CA too increases the speed of dehydration reaction.
Carbonic anhydrase also can be used for accelerating the carbonic acid gas in trapping amine aqueous solution.Preferably, amine material is selected from tertiary amine and/or ammonia.
Similar with solid carrier, the particle containing enzyme particle or polysilicates-silicone multipolymer coating that wherein carbonic anhydrase is embedded in polysilicates-silicone multipolymer can be used for catalysis for certainly containing CO 2gas remove CO 2process.
Usually, described method comprises the liquid of the suspension made containing enzyme containing granule and contains CO 2gas contact.Select suitable contactor to promote CO 2diffuse in liquid.Work as CO 2when diffusing in liquid, it and catalysis CO 2contacting containing enzyme particle of hydration, forms the treated liquid comprising hydrogen ion and bicarbonate ion thus.
For utilizing the typical reactor of suspension source property method to comprise batch reactor, semibatch and continuous flow reactor, as having packed tower and the dish contactor of random packing or structuring filling.
System design
Multiple reactor can be used for the carbon dioxide in hydration gas stream with the system forming bicarbonate ion, comprise packed bed, fluidized-bed or continuously stirring groove.When using packed bed or fluidized-bed reactor, the gas and the liquid stream that enter reactor can be and flow or counter-current configuration.For example, and in streaming system, gas and liquid stream the form of gas microbubbles in liquid stream can enter reactor.
The filler of reactor preferably comprises the carrier of the coating of immobilization carbonic anhydrase as above.
Or liquid stream can contain the suspension of polysilicates as above-silicone multipolymer immobilization carbonic anhydrase particle.
Structure in reactor can be similar with distillation tower, wherein makes with the surface contact of gas and liquid stream maximum by the packing material orientation comprising immobilization carbonic anhydrase.
In a particular system, two unit continuous-flow systems are used in CO 2hydration CO in resorber 2gas is to form bicarbonate ion and at CO 2bicarbonate ion is made to be dehydrated into CO in stripper 2, water and carbanion.Described unit can have packed tower design.The schematic diagram comprising this two cellular system of resorber 10 and stripper 12 is depicted in Figure 1A.CO 2gas stream 14 enters the bottom of resorber 10, and liquid stream 16 enters the top section of resorber 10.Liquid stream 16 is distributed in by sparger (not shown) on the top of the filler (not shown) of the middle portion of resorber 10.Liquid stream 16 makes the surface wettability of filler and is downward through resorber 10, and CO 2gas stream 14 upwards flows through the space in filler in a counter-current configuration relative to the flowing of liquid.Filler provides the contact area between liquid phase and gas phase, and comprises fixing carbonic anhydrase on its exterior.CO in gas stream 2by liquid-absorbent, and treated gas stream 18 leaves the top of resorber.When under liquid stream during tower, it is rich in CO 2, form bicarbonate radical, and treated liquid stream 20 leaves the bottom of resorber.Treated liquid stream 20 is pumped to the top section of stripper 12, and is distributed on filler by sparger (not shown).Bicarbonate radical in liquid stream 20 is converted to carbonic acid gas, water and carbonate.In order to produce CO 2this reaction speed of reaction by heating, decompression, in stripper, fix carbonic anhydrase, and by lower than air pressing operation with increase removing CO from stripper 12 2speed increase.Water and carbonate can recirculation and merging with the liquid stream 16 entering resorber 10, and carbonic acid gas leaves the top of stripper as gas stream 22 and can process further as required.
Or, resorber can have be fixed on carbonic anhydrase on standard reaction device packing material (as being generally used for Berl saddle packing in packed tower, Intalox saddle(packing), Raschig ring or Pall ring filler) and can with microvesicle CO 2gas and the contact of the carbonate aqueous solution are to make surface-area increase between gas and liquid by CO 2gas transfer is in the carbonate aqueous solution.
In addition, described system can comprise reactor 24 as shown in fig. 1b, and it has film 26, wherein containing CO 2gas stream 28 contact with the first surface 30 of described film and carbonate water solution flow 34 on the second surface 32 of film.Film at least can be CO 2gas permeated, but not can be 34 infiltrations of carbonate water solution flow or first surface 30 and not can be logistics 34 and permeated.Film 26 can support immobilization carbonic anhydrase as described herein.CO in gas stream 28 2gas can interact with immobilization carbonic anhydrase and change into bicarbonate radical.Bicarbonate radical diffuses through film 26 and is absorbed by logistics 34.Mould material can be polysaccharide, ion exchange resin, treated silicon oxide, porous metal structure, carbon-point or pipe, graphite fibre, silicon-dioxide bead, cellulose membrane, gelled matrix (such as polyacrylamide gelling, poly-(acryloyl morpholine) gelling, nylon wire etc.).High surface area/volume the membranous system that can be used in this structure is disclosed in U.S. Patent No. 6,524, in 843.
In another example, semibatch continuous-flow system can be used for removing CO from mixed flow 2gas, as is shown in fig. 1 c.Containing CO 2the mixture of gas enters groove TK-1, wherein CO 2be absorbed into and can contain in the liquid of the suspension of immobilized enzyme.Immobilized enzyme can be particulate forms further.Therefore, indicated by Fig. 1 C, at CO 2after conversion, liquid becomes and is rich in bicarbonate radical, and subsequently, CO 2the treated gas stream that level reduces moves from concentrated flow continuously.
Batch system can comprise the suspension of immobilized enzyme, and wherein enzyme is carbonic anhydrase and immobilization material comprises herein polysilicates-silicone multipolymer in greater detail.Therefore, above-mentioned semibatch continuous-flow system can containing the suspension of immobilization carbonic anhydrase particle with granularity as herein described, and wherein carbonic anhydrase is fixed in polysilicates-silicone multipolymer.
Immobilization carbonic anhydrase particle also can be fixed in the form of a particle and immobilization carbonic anhydrase particle can be fixed in the immobilization material obtained by the reaction of colloidal sol and catalyzer, described colloidal sol comprises (i) organoalkoxysilane or organotrialkoxysilane or metasilicic acid ester, (ii) poly-(silicone), and (iii) carbonic anhydrase.
Stripper optionally can have the charging being fixed on the carbonic anhydrase on standard reaction device packing material and the bicarbonate radical solution from resorber.In order to produce CO 2the speed of reaction of this reaction increase by heating and remove CO from stripper 2by increasing lower than air pressing operation.
Depending on application-specific or pending gas stream, these system designs can different tectonic association.For example, the system specification can about the CO of feed stream 2the temperature and pressure demand of content and the pollutant level needed for total purity, the rate of recovery and product stream and two kinds of logistics is customized.Compared to corresponding resolvase, use immobilized enzyme can increase the scope of system operating condition and reduce reactor size.Packed tower as described herein can be used as resorber and membrane reactor as described herein can be used as stripper.Or membrane reactor as described herein can be used as resorber and packed tower can be used as stripper as described herein.
In addition, system design can substantially as depicted in fig. 2.For example, carbon capture method unit comprises standard absorption unit and stripping (reactive distillation) unit.The core component of carbon trapping system (CCS) is absorptive unit operation, steam stripping unit operation and the heat exchange integral part between two unit operations.Peripherals can comprise standard control hardware and software, flow monitoring and adjusting device (such as control valve, under meter), pump, pH monitoring equipment (such as pH meter), temperature monitoring equipment (such as temperature monitor) or its any combination.Optional equipment can be provided for the means of monitor and forecast method.
Described system can comprise multiple reaction vessel, and wherein two or more reaction vessels contain the carrier of coating.
Carbonic anhydrase
Bicarbonate ion and proton is become for carbonic anhydrase (CA) the catalysis carbon dioxide conversion in system as herein described.The carbonic anhydrase be applicable to previously was described in this article.Also compound or the enzyme of the activity simulating carbonic anhydrase as above can be utilized.
Liquid
As mentioned above, make liquid and contain CO 2gas contact with helps absorption CO 2and the CO in increase liquid 2concentration.
Preferably, liquid comprises organic or mineral alkali.Alkali is proton acceptor.
Alkali can be metal hydroxides, quaternary ammonium hydroxide, metal carbonate, quaternary ammonium carbonate, quaternary ammonium alkoxide, metal amide, metal alkylide, metal alkoxide, Pure Silicon Metal alkanol hydrochlorate, amine (primary amine, secondary amine and tertiary amine), the conjugate base of amino acid, alkanolamine, weak acid or its combination.
Metal hydroxides can comprise lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, hydrated barta or its combination.In addition, ammonium hydroxide can be used in waterborne liquid.
Metal carbonate can be Quilonum Retard, sodium carbonate, salt of wormwood, rubidium carbonate, cesium carbonate, magnesiumcarbonate, calcium carbonate, Strontium carbonate powder, barium carbonate, volatile salt, organic cations carbonate or its combination.For example, organic cations carbonate can be carbonic acid tetra-allkylammonium (such as carbonic acid tetramethyl-ammonium, carbonic acid tetraethyl ammonium, carbonic acid tetrapropyl ammonium, carbonic acid TBuA, carbonic acid four pentyl ammonium or carbonic acid tetrahexyl ammonium), alkyl carbonate trimethyl ammonium (such as carbonic acid ethyl trimethyl ammonium, carbonic acid oxypropyl trimethyl ammonium, carbonic acid butyl trimethyl ammonium, carbonic acid amyl group trimethyl ammonium, carbonic acid hexyl trimethyl ammonium, carbonic acid heptyl trimethyl ammonium, carbonic acid octyl trimethyl ammonium, carbonic acid nonyl trimethyl ammonium, carbonic acid decyl trimethyl ammonium, carbonic acid dodecyl trimethyl ammonium or carbonic acid undecyl trimethyl ammonium), alkyl carbonate triethyl ammonium (such as methyl triethyl ammonium, carbonic acid propyl group triethyl ammonium, carbonic acid butyl triethyl ammonium, carbonic acid amyl group triethyl ammonium, carbonic acid hexyl triethyl ammonium, carbonic acid heptyl triethyl ammonium, carbonic acid octyl group triethyl ammonium, carbonic acid nonyl triethyl ammonium, carbonic acid decyl triethyl ammonium, carbonic acid dodecyl triethyl ammonium or carbonic acid undecyl triethyl ammonium), amino acid or its combination.
Quaternary ammonium hydroxide, quaternary ammonium carbonate or quaternary ammonium alkoxide can be hydroxide phenmethyl trimethyl ammonium, bursine, diethyldimethylammonhydroxide hydroxide, dimethyl dodecyl ethyl ammonium, two hydroxide N, N, N, N ', N ', N '-six butyl hexa-methylene two ammonium, hydroxide cetyltrimethyl ammonium, hydroxide hexamethonium, triethyl ammonium methyl, hydroxide tributyl-methyl phosphonium ammonium, hydroxide three hexyl four decyl ammonium, tetrapropylammonium hydroxide, tetrabutylammonium, hydroxide four (octadecyl) ammonium, hydroxide methyl tripropyl ammonium, ethanol TBuA, tetraethyl ammonium hydroxide, hydroxide tetrahexyl ammonium, hydroxide four (decyl) ammonium, tetramethyl ammonium hydroxide, hydroxide phenyl ammonium or its combination.
Metal amide, metal alkoxide or Pure Silicon Metal alkanol hydrochlorate can be tertiary amyl alcohol lithium, two (trimethyl silyl) acid amides lithium, diethylamide lithium, dimethylformamide lithium, LDA, two (trimethyl silyl) acid amides sodium, two (trimethyl silyl) acid amides potassium, dicyclohexyl acid amides lithium, lithium trimethylsilanolate, sodium methylate, potassium methylate, lithium methoxide, sodium ethylate, potassium ethylate, lithium ethoxide, isopropyl lithium alkoxide, sodium tert-butoxide, potassium tert.-butoxide, trimethyl carbinol lithium, sodium tert-amyl alcohol, tertiary amyl alcohol potassium, magnesium ethylate, two-tert-butyl alcohol magnesium, trimethyl silicane sodium alkoxide, trimethyl silicane potassium alcoholate or its combination.
Amine can be the cyclic amine of 2-(the chloro-6-fluorophenyl of 2-) ethamine, Isosorbide-5-Nitrae-diazabicyclo [2.2.2] octane ( 33-LV), 1, 5-diazabicyclo [4.3.0]-5-in ninth of the ten Heavenly Stems alkene, 1, 4-diazabicyclo [2.2.2] octane, 1, 8-diazabicyclo [5.4.0] 11-7-alkene, 4-(dimethylamino) pyridine, 2, 6-lutidine, piperidines, 1, 8-(dimethylamino) naphthalene, 2, 2, 6, 6-tetramethyl piperidine, 2, 8, 9-triisobutyl-2, 5, 8, 9-tetra-azepine-1-phosphabicyclo [3.3.3] undecane, tripelennamine (tripelennamine), aniline, benzene methanamine, methylphenylamine, imidazoles, pyrroles, pyridine, morpholine or its combination.
Amine can be primary amine, secondary amine, tertiary amine or its combination.
Primary amine can be methylamine, ethamine, propylamine, Isopropylamine, butylamine, isobutylamine, sec-butylamine, TERTIARY BUTYL AMINE, amylamine, isobutylcarbylamine, secondary amylamine, tertiary amylamine, hexylamine, dissident's amine, secondary hexylamine, tertiary hexylamine, quadrol, (2-methyl butyl) amine, 2-aminopentane, 3-(tert.-butoxy) propylamine, 2-amino-6-methylheptane, 1-ethylpropylamine or its combination.
In addition, secondary amine can be dimethylamine, diethylamine, dipropyl amine, dibutylamine, diamylamine, dihexylamine, methyl ethyl-amine, methyl propylamine, methylbutylamine, ethylpropylamine, ethyl butyl amine, N-ethyl dimethylamine, N-methylisopropylamine, N-butyl methylamine, N-ethyl isopropylamine, N-tertiary butyl methylamine, N-ethyl butyl amine, 3-isopropoxy propylamine, chlorine (diethylamino) dimethylsilane, 2, 2 '-(ethylenedioxy) two (ethamine), 1, two (chloromethyl)-1 of 3-, 1, 3, 3-tetramethyl-disilane base alkane, N-tertiary butyl Isopropylamine, N, N-diethyl trimethyl silyl amine, di-sec-butylamine or its combination.
In addition, tertiary amine can be Trimethylamine 99, triethylamine, tripropyl amine, Tributylamine, dimethyl amine, dimethyl propylamine, dimethyl butylamine, diethyl methyl amine, diethyl propylamine, diethyl butylamine, N, N-diisopropyl methylamine, N-ethyl diisopropylamine, N, N-dimethyl amine, N, N-diethyl butylamine, 1,2-dimethyl propylamine, N, N-diethyl methyl amine, N, N-dimethylisopropylamine, 1,3-dimethyl butylamine, 3,3-dimethyl butylamine, N, N-dimethyl butylamine or its combination.
Alkanolamine can be 2-amino-2-(hydroxymethyl)-1,3-PD ( alkali), Propanolamine, thanomin, diethanolamine, dimethylethanolamine, N-Mono Methyl Ethanol Amine, trolamine or its combination.
The conjugate base of weak acid can be acetate moiety, citrate, amber acid radical, oxalate, malate, malonate, phosphate radical, phosphonate radical, sulfate radical, thionamic acid root or its combination, wherein counter ion can be positively charged ion, as basic metal, alkaline-earth metal, ammonium cation or its combination.
Preferably, liquid comprises waterborne liquid.
When liquid is waterborne liquid, alkali is water miscible and does not make carbonic anhydrase sex change.
Unless otherwise instructed, otherwise the alkyl as herein described preferably low alkyl group of containing 1 to 8 carbon atom and at the most 20 carbon atoms in main chain.Alkyl can be substituted or not be substituted and can be straight or branched.The example of unsubstituted alkyl comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, sec-butyl, the tertiary butyl, n-pentyl, isopentyl, sec.-amyl sec-pentyl secondary amyl, tert-pentyl etc.As the term " replacement " in " alkyl of replacement " refers to that the various heteroatomss as oxygen, nitrogen, sulphur, phosphorus etc. or can be connected to the carbon atom of alkyl in main chain as side base.For example, the alkyl of replacement can have-C-X-C-fragment in main chain, and wherein X is heteroatoms.In addition, at least one of the alkyl of replacement is incorporated into the hydrogen atom of carbon atom can by one or more substituting group, as displacements such as hydroxyl, alkoxyl group, alkyl sulfenyl, phosphino-, amino, halogen, silyl, nitro, ester, ketone, heterocycle, aryl.
Abbreviation " PDMS " represents polydimethylsiloxane, abbreviation " PDMS550 " represents the polydimethylsiloxane with 550 daltonian molecular-weight average, abbreviation " TMOS " represents tetramethoxy-silicane or tetramethylorthosilicate, abbreviation " PEG460 " represents the polyoxyethylene glycol with 4600 dalton's molecular-weight average, and abbreviation " MTMOS " represents methyltrimethoxy silane.
Now describe the present invention in detail, by aobvious and easy to know be do not departing from claim of enclosing under the scope of the present invention limited, modifications and variations are possible.
Accompanying drawing is sketched
Figure 1A and 1B is and CO 2the CO of stripper coupling 2the schematic diagram of resorber and Fig. 1 C are the schematic diagram of semibatch reactor.
Fig. 2 is the schematic diagram of the ring-closure reaction device utilized in embodiment 21,28 and 30.
Fig. 3 is the FTIR of the polysilicates/polysiloxane dry gel powder containing CA/18-hat-6 using the synthesis program in embodiment 4 to produce.
Fig. 4 is containing the BET Nitrogen adsorption isotherm of representative dry gel powder sample.
Fig. 5 contains the figure of the BJH pore size distribution in the representative dry gel powder sample of display.
Fig. 6 shows the SEM image of the dry gel particle containing 18-hat-6 using the synthesis program described in embodiment 3 to produce.
Fig. 7 shows the weight percent specific inventory research of the polysilicates/polysiloxane xerogel containing CA/18-hat-6 using the synthesis program in embodiment 4 to produce.
The circulation that 0.2 % by weight suspension suspension of the particle that Fig. 8 display is prepared by the synthetic method described in use embodiment 2 flows carried out in 1/8 inch of Tipton Ceramic Balls is tested.
Fig. 9 A-D is the scanning electron photomicrograph of the polysilicates-silicone Copolymer Emulsion Coating under 25x, 1000x, 2500x and 5000x magnification in Ceramic Balls respectively.
Figure 10 is the diagram of carbonic anhydrase load level on the impact of the gained enzymic activity of the carrier of the coating prepared by embodiment 13.
Figure 11 is the diagram of deposit multilayer polysilicates-silicone copolymer layer on the impact of the gained enzymic activity of the carrier of the coating that the catalysis that the use surface of being prepared by embodiment 18 is caused produces.
Figure 12 is the diagram of the catalytic activity of the Tipton carrier of coating prepared according to the method for general introduction in embodiment 18, and described catalytic activity is shown as CO 2conversion percentages and the enhancing multiplier exceeding exposed ceramic filling material.
Figure 13 display as described in example 18 above, goes through catalytic activity and the paint thickness of the carrier of the coating that 366 days measure in ring-closure reaction device.
The figure that Figure 14 sample enzyme in time of three coatings containing the polysilicates source property coating being embedded with carbonic anhydrase that to be display prepare according to embodiment 18 retains, described reservation be as continue 42 days in Continuous Flow environment measure (as described in example 18 above).
Figure 15 is that the carrier of the coating that display is prepared according to embodiment 18 is at contaminant trace species SO 2and NO 2the figure of the catalytic activity under existing.
Figure 16 is that the carrier of the coating that display is prepared according to embodiment 18 is at the figure using the catalytic activity under coal combustion flue gas.
Figure 17 shows the coating 2 using the preparation described in embodiment 26 and method coating " K of Sulzer filler unit g.
Figure 18 is presented at and utilizes 0.051 % by mole of NH 42 of the preparation described in embodiment 26 and method coating are used under F catalyzer " paint thickness of Sulzer structurizing packing material research (being described as quality).
Figure 19 show use 2 of the preparation described in embodiment 27 and method coating " K of Sulzer filler unit g.
2 of sticking method coating described in the use embodiment 29 that Figure 20 display utilizes the dry gel powder using methanol dilution legal system standby to produce according to embodiment 3 " K of Sulzer filler unit g.
2 of sticking method coating described in the use embodiment 29 that Figure 21 display utilizes the dry gel powder using alcohol dilution legal system standby to produce according to embodiment 7 " K of Sulzer filler unit g.
2 of sticking method coating described in the use embodiment 29 that Figure 22 display utilizes the dry gel powder using phosphate buffered saline buffer dilution method to prepare to produce according to embodiment 1 " K of Sulzer filler unit g.
Whole graphic in corresponding reference signs instruction corresponding component.
Embodiment
There is provided following non-limiting example to further illustrate the present invention.
embodiment 1: under 18-hat-6 exists, synthesis and embedding carbonic anhydrase are in polysilicates/Silicone particles
In an exemplary program, load tetramethylorthosilicate (2.6mL, 17.6mmol), silanol stopped poly-(dimethyl siloxane) (average M to 100 mL beakers w=550; 2.2mL) be preced with-6-ether (600mg, 2.3mmol) with 18-.Vigorous stirring mixture is preced with-6-ether to dissolve 18-completely in 5 minutes.
Individually, preparation 150mg/mL carbonic anhydrase (carbonic anhydrase, NS81239 are supplied by Novozymes A/S, Denmark) stoste in 10mM phosphate buffered saline buffer (pH=7.2).
Then, to add in 2.4mL reserve A to reaction beaker and vigorous stirring gained heterogeneous mixture to produce the emulsion of fine dispersion.
Then, the 1M NH of 112 μ L is added 4the F aqueous solution is in reaction vessel.Stirred the mixture 2 minutes by magnetic agitation subsequently, or until start to observe gelling.After stirring 2 minutes, beaker contains no longer by stirring the highly viscous polymeric material mixed.
Then at room temperature dry polymeric material 1 hour.After 1 hour, beaker is transferred in 55 DEG C of baking ovens and continues 24 hours, after this, make temperature be increased to 75 DEG C and continue 72 hours.
After solidification, collect powder, use mortar and pestle, and then obtain dry substance.
In some cases, after acquisition dry substance, use a series of sieve according to size separation bulk powder.
To there is the powder of desired particle size at 0.8M/1.2M K under stirring/stirring 2cO 3/ K HCO 3hydration 72 hours in damping fluid (under pH=10.0).Then by collecting by filtration particle, and the aliquots containig of collection stoste is to measure the reservation of enzyme in particle.
These particles are then with fresh 0.8M/1.2M K 2cO 3/ KHCO 3damping fluid (under pH=10.0) fully washing and dry or be stored in 0.8M/1.2M K 2cO 3/ KHCO 3in damping fluid (under pH=10.0).
embodiment 2: the synthesis of phosphate buffered saline buffer dilution under 18-hat-6 exists and embedding carbonic anhydrase are in polysilicates/Silicone particles
In an exemplary program, load 150mg/mL carbonic anhydrase (carbonic anhydrase, NS81239 are supplied by Novozymes A/S, the Denmark) stoste of 2.4mL to 100mL beaker, then add the 100mM phosphate buffered saline buffer of 5.0mL and fully mix.
Then, add under vigorous stirring (or vortex) containing tetramethylorthosilicate (2.6mL, 17.6mmol), silanol stopped poly-(dimethyl siloxane) (average M w=550; 2.2mL) be preced with the solution of-6-ether (0.6g, 2.2mmol) with 18-.
Add the 1M NH of 112 μ L volumes 4the F aqueous solution is in reaction vessel.Stir the mixture subsequently until start to observe gelling.
Then the program Solidification described in embodiment 1 and hydrated sample is followed.
embodiment 3: 18-hat-6 exist under methanol dilution synthesis and embedding carbonic anhydrase in polysilicates/Silicone particles
In an exemplary program, 150mg/mL carbonic anhydrase (the carbonic anhydrase of 12mL is loaded in 400mL beaker, NS81239, by Novozymes A/S, Denmark supplies) stoste, then add under vigorous stirring (or vortex) containing tetramethylorthosilicate (13mL, 88mmol), silanol stopped poly-(dimethyl siloxane) (average M w=550; 11mL) be preced with the solution of-6-ether (3g, 11mmol) with 18-.
After effectively disperseing and emulsion is formed subsequently, add 15mL reagent-grade methanol.The 1M NH of 0.5mL is added at once after adding methyl alcohol 4f is in stirring the mixture.After the 30 seconds, mixture starts thickening, and observes gelling in about 30 minutes.
Use the same program retained for thermofixation, hydration and detection enzyme described in embodiment 1 herein.
embodiment 4: 18-hat-6 exist under methanol dilution synthesis and embedding carbonic anhydrase in polysilicates/Silicone particles; Substituting order of addition
In an exemplary program, in 400mL beaker, load 150mg/mL carbonic anhydrase (carbonic anhydrase, NS81239 are supplied by Novozymes A/S, the Denmark) stoste of 12mL, then, under agitation add the 1M NH of 0.5mL 4f is in enzyme solution.
By combination tetramethylorthosilicate (13mL, 88mmol), silanol stopped poly-(dimethyl siloxane) (average M w=550; The independent stoste (reserve B) of organic monomer 11mL) is prepared with 25mL methyl alcohol.
Individually, prepare 18-and be preced with-6 (3g, 11mmol; Reserve C) and the stoste of 25mL reverse osmosis (RO) water.
Then merge stoste B and C and be added into vigorous stirring in the beaker containing enzyme.Mixture starts fast thickening, and observes gelling in about 30 seconds.
Use the same program retained for thermofixation, hydration and detection enzyme described in embodiment 1 herein.
embodiment 5: PEG exist under methanol dilution synthesis and embedding carbonic anhydrase in polysilicates/Silicone particles
Similar to Example 4, in 400mL beaker, load 150mg/mL carbonic anhydrase (carbonic anhydrase, NS81239 are supplied by Novozymes A/S, the Denmark) stoste of 12mL, then, under agitation add the 1M NH of 0.5mL 4f is in enzyme solution.By merging tetramethylorthosilicate (13mL, 88mmol), silanol stopped poly-(dimethyl siloxane) (average M w=550; The independent stoste (reserve B) of organic monomer 11mL) is prepared with 25mL methyl alcohol.
Individually, polyoxyethylene glycol M is prepared r=570-630) (3g; Reserve C) and the stoste of 25mL RO water.
Then merge stoste B and C and be added into vigorous stirring in the beaker containing enzyme.Mixture starts fast thickening, and observes gelling in about 30 seconds.
Use the same program retained for thermofixation, hydration and detection enzyme described in embodiment 1 herein.
This program is also for the preparation of containing polyoxyethylene glycol (typical M n=4,600), polyoxyethylene glycol (typical M n=8,000) and poly-(oxyethane) (approximate M w=100,000) derivative.
embodiment 6: 18-hat-6 exist under methanol dilution synthesis and embedding carbonic anhydrase in polysilicates/Silicone particles time be incorporated to hydrophobic additive
Similar to Example 3,150mg/mL carbonic anhydrase (the carbonic anhydrase of 12mL is loaded in 400mL beaker, NS81239, by Novozymes A/S, Denmark supplies) stoste, then, load under vigorous stirring (or vortex) containing tetramethylorthosilicate (11.8mL, 80mmol), trimethoxymethylsila,e (1.14mL; 8mmol), silanol stopped poly-(dimethyl siloxane) (average M w=550; 11mL) be preced with the solution of-6-ether (3g, 11mmol) with 18-.
In effective dispersion, after forming emulsion subsequently, add 15mL reagent-grade methanol.The 1M NH of 0.5mL is added at once after adding methyl alcohol 4f is in stirring the mixture.
Gelling is observed in about 30 minutes.
Use the same program retained for thermofixation, hydration and detection enzyme described in embodiment 1 herein.
This program is also for the preparation of the xerogel containing derivative, and it is isobutyl-(trimethoxy) silane of 1: 10 mol ratio, normal-butyl (trimethoxy) silane and n-octyl (trimethoxy) silane that described derivative contains with tetramethylorthosilicate.
embodiment 7: 18-hat-6 and CTAB exist under alcohol dilution synthesis and embedding carbonic anhydrase in polysilicates/Silicone particles
In an exemplary program, 150mg/mL carbonic anhydrase (the carbonic anhydrase of 3.6mL is loaded in 250mL beaker, NS81239, by Novozymes A/S, Denmark supplies) stoste, to in this enzyme solution, add 0.15g cetyl trimethylammonium bromide (CTAB, 0.4mmol) and stir and dissolve completely to reach.
Then, add under vigorous stirring (or vortex) containing tetramethylorthosilicate (3.9mL, 26mmol), silanol stopped poly-(dimethyl siloxane) (average M w=550; 3.3mL) be preced with the solution of-6-ether (0.9g, 3.3mmol) with 18-.After effectively disperseing and emulsion is formed subsequently, add the 0.1M NH of 4.5mL 4f is in stirring the mixture.
Mixture gets started and becomes opaque, and adds 27mL reagent alcohol (90% ethanol, 5% methyl alcohol, 5% Virahol) fast with vigorous stirring.
After 10-15 second, this mixture starts thickening, and second aliquots containig of under agitation adding 7.5mL reagent alcohol is to contribute to shifting mixture.
Then by its impouring kiver (6 " × 6 " × 1 ") in and make its at room temperature dried overnight.
Next day, container to be seated in 75 DEG C of baking ovens 72 hours.
Use the same program retained for powder processing, hydration and detection enzyme described in embodiment 1 herein.
embodiment 8: characterize the polysilicates/Silicone particles containing carbonic anhydrase
The representative FTIR spectrum of the particle using the synthetic method described in embodiment 4 to produce is shown in Fig. 3.Characteristic peak corresponding to Si-O bonding sees 794cm -1and 1013cm -1place.In addition, at 1257cm -1and 2960cm -1the peak at place indicates and is successfully incorporated to PDMS.Immobilized enzyme display is from 1375cm -1to 1680cm -1a series of peaks.These spectral signatures see in the dry gel powder using the combination of tetramethylorthosilicate, polydimethylsiloxane and carbonic anhydrase to prepare with the ratio described in embodiment 1 to 7 usually.
Usually, 18-hat-6 and being incorporated to not by FTIR Analysis and Identification of polyoxyethylene glycol, because their principal character peak is overlapping by other component of matrix.
A series of representative Bruner-Emmett-Teller (Brunner-Emmett-Teller, the BET) Nitrogen adsorption isotherm of the sample collection prepared according to the experimental arrangement described in embodiment 3 (AJL-03-33B, BMR-3-92, BMR-04-011a, DCP-10-56-4, LW-6-54a and TA-a33-48A) and embodiment 7 (A5L-0-23) is shown in Fig. 4.Average surface area (m 2/ g) at 5.83 to 18.42m 2in the scope of/g, wherein the mean value of surface-area is 10.4m 2/ g.
As shown in Figure 5, by preceding sample being carried out to Barrett-Joy Na-Ha Lunda (Barrett-Joyner-Halenda, BJH) analyze the pore volume distribution show hole volume (cc/g) obtained in the scope of 0.0344 to 0.172, the average pore sizes wherein calculated is 0.059cc/g.
Analyze by above-mentioned BJH the bore dia obtained and show median pore size in the scope of 10nm to 80nm.
The sample (A5L-0-23) prepared according to the method in embodiment 7 shows the long-pending (18.42m of highest face temperature in this series 2/ g) and pore volume (0.172cc/g).
A series of scanning electron microscopy images (SEM) of the sample prepared according to the program in embodiment 3 are shown in Fig. 6.Roomy the causing between 10 to 20 μm of presentation graphics display particle coacervation thing.Condensation product seems primarily of less primary particle composition.
embodiment 9: to the active testing of the polysilicates/Silicone particles containing carbonic anhydrase in batch reactor
For the activity of polysiloxane/polysilicates particle of test containing carbonic anhydrase, prepare suspension under the particle of Different Weight per-cent and being tested in batch reactor system.
Batch reactor forms by adding the sealed vessel be pressed between 60 and 100psig.Feed gas is by with N 2the 15%CO of counterweight 2composition.At room temperature carry out experiment as herein described.
Use mechanical stirring bar mixing gas phase, and use magnetic stirring bar blended liquid phase.The mixing of liquid is enough slowly to make surface-area remain unchanged at whole experimental session.
With CO 2mixture goes through the pressure drop of monitoring 10 minute period in container after loading container.Use the CO of known mole number in container 2, pressure and solution surface amass, and calculates the K of suspension gand use mmol/sm 2kPa represents.
Usually, at the 0.8M/1.2M K of 100mL 2cO 3/ KHCO 3in damping fluid (under pH=10.0), under the weight percent specific inventory of the enzyme existed in altering reactor and/or quantity, test sample.
Table 1 shows the activity of some representative samples prepared according to the method described in embodiment 1 to 7.The synthetic method of the examples representative broad range shown in table 1, preparation, weight percent specific inventory and processing.
The activity of table 1-polysilicates/Silicone particles in batch reactor
No. 1 entry in table 1 is the representative negative control prepared by the synthesis program described in embodiment 3, but phosphate buffered saline buffer is used for supplementing enzyme carbonic anhydrase.The relative K of this sample g0.012mmol/sm 2kPa, this is similar to blank solution (the average K not containing catalyzer g=0.011mmol/sm 2kPa).This result clearly indicates the xerogel particles without carbonic anhydrase not accelerate CO 2absorb in test soln.
2-13 entry in table 1 describes the activity according to the sample of preparation under carbonic anhydrase exists of the method described in embodiment 1 to 7.Except No. 12 entries, all samples all shows the considerable enhancing exceeding blank solvent.
Hydroxy-end capped PDM S is there is not in No. 12 entry displays in table 1 according to embodiment 2 550the sample of lower preparation.After washing and hydration, quantitatively showing almost without until do not have enzyme to be encapsulated in excess silicon acid esters particle enzyme.This obviously shows with pole low activity under 0.2 % by weight xerogel loading capacity.
In the figure 7, the representative loading capacity research of the sample prepared according to the synthetic method described in embodiment 4 is shown.Similar characteristics is observed in multiple loading capacity research.
embodiment 10: to the active testing of the polysilicates/Silicone particles containing carbonic anhydrase in counter-current tower.
For assessing the use of these particles in flow through reactors, by the pumping of Different Weight percent solution at random (Tipton1/8 inch pottery) and structuring filling (Sulzer 500X, has 2 " tower diameter) on.
In fig. 8, use peristaltic pump under speed control (20 ml/min) by the particle prepared according to embodiment 2 in 0.8M/1.2M K 2cO 3/ KHCO 30.2 % by weight suspension in damping fluid (under pH=10.0) (exception part is that it is containing 18-hat-6) from the top pumping of tower in 1/8 inch of Tipton Ceramic Balls of 65g.Comprise 15%CO 2(use N 2counterweight) gas upwards flow from the bottom of tower.Use monitoring at the CO of the output of tower 2the non-dispersive infrared detector (NDIR) of gas comes CO 2conversion is carried out quantitatively.Export the CO of gas 2content is relative to the CO of feed gas 2difference between content is for calculating uptake rate.
Continue within about 20 minutes, to carry out the research in Fig. 8.Under sample is presented at 0.2 % by weight loading capacity, average K g0.051mmol/sm 2kPa.As shown in blue trace, exposed Tipton ceramic packing shows 0.015mmol/sm 2the average K of kPa g, this represents that exceeding blank filler accelerates about 3.3 times.
In a similar experiment, analyze 1.2 % by weight suspension of particle prepared according to embodiment 1 activity in 1/8 inch of Tipton Ceramic Balls 20 minutes.Sample shows 0.08mmol/sm 2the stable state K of kPa g, it corresponds to K gexceed blank improvement about 6 times.
In one separately experiment, in circulation research, have 2 " Sulzer of tower diameter upper 0.4 % by weight sample analyzed the method described in embodiment 3 of use and prepare of 500X.By the top pumping of suspension from tower under speed control (218 ml/min).Comprise 15%CO 2(use N 2counterweight) gas upwards flow (2.18SLPM) from the bottom of tower.By the average K of 0.4 % by weight suspension gbe calculated as 0.0358mmol/sm 2kPa, this corresponds to mean rate enhancing (multiplier) of 2.78.
embodiment 11: HF corrodes ceramic monolith
Load 1/8 inch of Ceramic Balls (Tipton Corp.) of 2600g to 5000mL plastic tank, and cover with the 10%HF aqueous solution of 2L subsequently.Within first 3 hours every 0.5 hour, use large plastic spatula hand operated mixing solution.Then make solution shelve under room temperature and environmental stress to spend the night, cover with plastic cover simultaneously.
At 24 hours later, decant HF solution, and the water of Ceramic Balls reverse-osmosis treated washs 3 times through sieve.After wash, before further use at 80 DEG C by dry 24 hours of each ball.
embodiment 12: hydrogen peroxide/ammonium hydroxide corrosion ceramic monolith
Load 1/8 inch of Ceramic Balls (Tipton Corp) of 1000g to 2500mL PYREX beaker, and use the H of 900mL water, 300mL subsequently 2o 2(30% aqueous solution) and 300mL ammonium hydroxide (28-30%w/w A.C.S. level reagent) cover.Heated solution to 80 DEG C and carry out a hand operated mixing for every 0.5 hour and continue 3 hours on hot plate.After 3 hours, decant etchant solution, and the water of Ceramic Balls reverse-osmosis treated washs 3 times through sieve.
After wash, before further use at 80 DEG C by dry 24 hours of each ball.
embodiment 13: make use NH 4f catalyzer is used for the immobilization carbonic anhydrase coated ceramic ball in the polysilicates/polysiloxane copolymer containing 18-hat-6
Tetramethylorthosilicate (2200 μ L, 14.9mmol), silanol stopped poly-(dimethyl siloxane) (average M is loaded to 600mL beaker w=550; 2200 μ L) and 18-hat-6-ether (600mg, 2.3mmol).Supersound process mixture 5 minutes is to homogenize.
Then, to add in 1600 μ L reserves A (as described in example 1 above) to reaction beaker and supersound process gained heterogeneous mixture 1 minute, or until observe the emulsion of fine dispersion.
The 1M NH of 112 μ L is added at once after supersound process 4the F aqueous solution is in reaction vessel.
Then add rapidly the Ceramic Balls (65g) of corrosion in reaction beaker, and subsequently mixture metal spatula is stirred 2 minutes, or until start to observe gelling.
After gelling starts, the pottery of coating to be distributed on mesh screen and each ball of uniform intervals is minimum to guarantee the contact before the drying between each.Then the mesh screen of Ceramic Balls containing coating to be transferred in baking oven (temperature set points is at 55 DEG C) and to make its dry 24 hours.
Make bead at 50mL damping fluid (0.8M/1.2M K 2cO 3/ KHCO 3damping fluid, under pH=10.0) middle dipping/balance 48 hours.The Ceramic Balls of coating rinses 3 times to remove the protein of leaching with water subsequently, and is stored in 50mL damping fluid (0.8M/1.2M K 2cO 3/ KHCO 3damping fluid, under pH=10.0) in
embodiment 14:make use NH 4f catalyzer is used for containing the immobilization carbonic anhydrase coated ceramic ball in the polysilicates/polysiloxane copolymer of tensio-active agent
Tetramethylorthosilicate (2200 μ L, 14.9mmol) and silanol stopped poly-(dimethyl siloxane) (average M is loaded to 600mL beaker w=550; 2200 μ L).Supersound process mixture 5 minutes is to homogenize.
Then, 1600 μ L reserves A (as described in example 1 above) and TRITON X-100 tensio-active agent (200 μ L, 0.2mmol) are merged, vortex subsequently.Subsequently this solution is added in reaction beaker, and supersound process gained heterogeneous mixture 1 minute (or until observing the emulsion of fine dispersion).Similar research is carried out with Tween20 and with cetyl trimethylammonium bromide.
The 1M NH of 112 μ L is added at once after vortex 4the F aqueous solution is in reaction vessel.
Then add rapidly the Ceramic Balls (65g) of corrosion in reaction beaker, and subsequently mixture metal spatula is stirred 2 minutes, or until start to observe gelling.
Drying for these samples is identical with the method used in embodiment 13 with hydration process.
embodiment 15: characterize and make use NH 4the pottery with single silicon-dioxide/enzyme coating that F catalyzer produces
Use the sample of the Ceramic Balls of the method preparation coating described in embodiment 13.By carrying out substance weight analysis to calculate the quality of the silicon-dioxide/enzyme coating being adhered to sample surfaces before coating and after drying.Calculate according to these, on average about 2 grams of materials are added into the surface of Ceramic Balls.The quality of coating is usually in the scope of 1.5g to 2.5g.In view of the surface-area of Ceramic Balls, measuring average film thickness is 25 μm.Film thickness is usually in the scope of 15 to 35 μm.The method described in embodiment 13 of use, the average CA loading capacity be determined on packing material is often liter of filler 1.9g CA.CA loading capacity is usually in the scope of often liter of filler 1.3 to 2.5g CA.
By the further sign using scanning electron microscopy (SEM) to obtain the packing material to silicon-dioxide/enzyme coating, as shown in Fig. 9 A-D.As seen in Figure 9, gained polysiloxane/polysilicates coating has medium high surface area (Fig. 9 B) and there is porous sign (Fig. 9 C and 9D).In addition, low magnification view is presented at coating in Ceramic Balls very homogeneous in nature and effectively cover whole surface (Fig. 9 A).
embodiment 16: utilize and make use NH 4the activity research with the pottery of single silicon-dioxide/enzyme coating that F catalyzer produces
For testing the intrinsic activity of multiple coating preparation in 1/8 inch of Ceramic Balls (Tipton Corp.), building and utilizing single pass reactors (SPR).SPR analytical system is served as small-scale absorption tower and is not used stripping tower to carry out regenerated solvent.The Ceramic Balls of coating is filled to 78.5cm high × 5/8 inch of internal diameter counter-current tower in.0.8M/1.2M K is applied with the speed of 20 ml/min from the top of tower at 30 DEG C 2cO 3/ KHCO 3damping fluid (under pH=10.0), and 15%CO 2gas (uses N 2counterweight) move up from the bottom of tower.By the CO of non-dispersive infrared detector (NDIR) monitoring at the output of tower 2the amount of gas, and the CO exporting gas 2content is relative to the CO of feed gas 2difference between content is for calculating uptake rate.
In an exemplary program, daily inspection is carried out to NDIR analyzer.If analyzer is not satisfied with requirement, calbiration system (15%CO so again 2calibration).
On average, 1/8 of 65g is applied by the sol gel processing described in embodiment 13 " Ceramic Balls (Tipton Corp.).
After 48 hours and two hydration/cycles of washing, decant buffered soln, and Ceramic Balls is loaded in reaction tower.Reaction tower contains mesh screen to prevent each ball whole process through tower.Between the top of tower and the sanitary fixture at bottom place, with O shape ring, tower is fixed on appropriate location.Use clip that tower is fixed on appropriate location at the top of device and bottom place, and liquid dispenser is inserted in tower close to center as far as possible.Start CO 2gas flow, set up required pressure, and NDIR reaches stable state.Start liquid flowing (usual 20 ml/min).Use pre-designed LABVIEW program stored in experimental data, simultaneously the manual reading stored in NDIR, pH and temperature.
Based on CO 2the value transformed (namely exports CO 2% by mole) calculate enzymic activity and be reported as conversion % and overall mass transfer coefficient (K g(mmol/sm 2kPa).
Table 2 shows the CO of the some preparations using the program described in embodiment 13 to produce 2transformation efficiency, KG and the KG of enzymatic reaction and the ratio (multiplier) of the KG contrasted.Comparatively speaking, exposed (uncoated) Ceramic Balls transforms average 8.4%CO in the steady state 2, this corresponds to 0.0145mmol/s-m 2the K of-kPa g.
table 2: the SPR of the Ceramic Balls of silicon-dioxide/enzyme coating is analyzed.
The hydrophobic nature of gained silicon-dioxide enzyme coating makes 24 hours hydration times be not enough to reach balance usually.The hydration time of 48 and 72 hours seems more effectively to transform CO 2, supposition is better moistening owing to observing in such systems.
Figure 10 shows the impact of enzyme loading capacity on activity.Loading capacity in Figure 10 is reported as the per-cent of enzyme quality corresponding to the coating of every quality.The enzyme loading capacity in these samples is changed by the concentration reducing the CA in phosphate buffered saline buffer during immobilization process.Use phosphate buffered saline buffer thing as an alternative, do not deposit the sample display K prepared in the context of enzymes gfor 0.02mmol/sm 2kPa.Polysilicates in mass containing 3% enzyme/polysiloxane coating materials display K gfor 0.05mmol/sm 2kPa, and the polysilicates/polysiloxane coating materials display K in mass containing 6% enzyme gfor 0.09mmol/sm 2kPa.Utilizing under the material using the program in embodiment 13 to produce, high enzyme loading capacity is no more than 0.1mmol/sm usually 2the K of kPa g.
Also studied the CO that 18-hat-6 is observed the ceramic packing of coating 2the effect of conversion capability.Not not hydrophobic containing the sample of crown ether and demonstrate 3 times that activity is uncoated pottery at the most.
In one separately research, 18-is preced with-6 ether hydrophilic polymers, comprises poly-(vinyl alcohol) (PVA), PEG (PEG) and the polymkeric substance containing polyquaternary amine (PQA) (i.e. poly-(diallyldimethylammonium chloride)) and replaces.Use these additives with the similar mol ratio (i.e. monomer/additive) of mol ratio being preced with-6 with 18-, and applied by the program described in embodiment 13.The pottery of gained coating does not retain their high enzymatic activity.
embodiment 17:the catalysis caused by surface is for the immobilization carbonic anhydrase coated ceramic ball in the polysilicates/polysiloxane copolymer containing 18-hat-6
Herein with the NH dissolved 4the catalysis that F (namely directly adding catalyzer in monomer solution) carries out is different from the catalysis caused on surface, wherein pottery NH 4f catalyst pretreatment takes off proton to induce ceramic silicon alkanol functional group.
In exemplary program, in 100mL sample cup for liquid, by 1/8 of 65g " diameter ceramic ball (Tipton Corp.) is immersed in the 91mM NH of 5.5mL 4in the F aqueous solution 5 minutes.After five minutes, ceramic for filtration ball on mesh screen.
Individually, tetramethylorthosilicate (2200 μ L, 14.9m mol/, silanol stopped poly-(dimethyl siloxane) (average M is loaded to 600mL beaker w=550; 2200 μ L) and 18-be preced with-6-ether (600mg, 2.3mmol) mixture.Supersound process mixture 5 minutes is to homogenize.
Then, to add in 1600 μ L reserves A (as described in example 1 above) to reaction beaker and supersound process gained heterogeneous mixture 1 minute, or until observe the emulsion of fine dispersion.
Then add rapidly the Ceramic Balls (65g) of catalyst treatment in reaction beaker, and mixture is stirred 2 minutes with metal spatula subsequently, or until start to observe gelling.
After gelling starts, the pottery of coating to be distributed on mesh screen and each ball of uniform intervals is minimum to guarantee to contact before the drying.The ceramic packing making coating at room temperature dry 15 minutes.Drying used and hydration process are similar to the method described in embodiment 13.
embodiment 18: the catalysis caused by surface is plane SH wave polysilicates-silicone copolymer coating in Ceramic Balls
By the 91mM NH of 65g Ceramic Balls (Tipton Corp.) with 5.5mL 4f aqueous solution process 5 minutes, and then shift on mesh screen to carry out drying.
Individually, tetramethylorthosilicate (2200 μ L, 14.9m mol), silanol stopped poly-(dimethyl siloxane) (average M is loaded to 600mL beaker w=550; 2200 μ L) and 18-be preced with-6-ether (600mg, 2.3mmol) mixture.Supersound process mixture 5 minutes is to homogenize.
Then, to add in 1600 μ L reserves A (as described in example 1 above) to reaction beaker and supersound process gained heterogeneous mixture 1 minute, or until observe the emulsion of fine dispersion.
Then add rapidly the Ceramic Balls (65g) of Neutral ammonium fluoride process in reaction beaker, and subsequently mixture metal spatula is stirred 2 minutes, or until start to observe gelling.
The ceramic packing making coating at room temperature dry 15 minutes.
After 15 min, the ceramic packing of coating is immersed in again the 91mM NH of 5.5mL 4in the F aqueous solution 5 minutes and according to the coating of above-mentioned program second layer collosol intermixture.During the applying second layer, to stir the mixture compared with slow rate to make the shearing force on the first layer minimum.After the applying second layer, the filler of at room temperature dry coating 30 minutes.Then the 3rd coating is applied according to previously described program.After applying the 3rd coating, the mesh screen of Ceramic Balls containing coating to be transferred in ventilated drying oven and to store 72 hours at 55 DEG C.
The quality of coating is calculated and the amount for calculating transfer efficiency, film thickness and immobilized enzyme in gravimetric analysis mode.
After the dry coating of acquisition after quality, add 50mL damping fluid (0.8M/1.2M K 2cO 3/ KHCO 3damping fluid, under pH=10.0) to plastic containers, make each ball flood/balance 68 hours in the solution.
Each ball rinses 3 times with water subsequently, then supplements 50mL damping fluid (0.8M/1.2M K 2cO 3/ KHCO 3damping fluid, under pH=10.0) solution.Before sign and active testing, repeat this washing procedure reach 3 times.
In mass, the enzyme/monomers/water ratios of the sol preparation of above display is 1: 15: 5.This ratio easily through the amount increasing or reduce monomer (i.e. tetramethylorthosilicate and poly-(dimethyl siloxane)), or can be changed by the volume increasing or reduce the proenzyme liquid be added in sol preparation.In addition, in sol preparation, the above ratio being shown as the monomer/hydrophilic additive of 45: 1 (with molar basis) can change in a similar manner.
embodiment 19: the pottery with single silicon-dioxide/enzyme coating characterizing the catalysis using surface to cause
The sample prepared of the method described in embodiment 18 of use demonstrates coating quality and enzyme loading capacity higher than the coating only containing single silicon-dioxide/enzyme material coating.
The average about 5.3 grams of materials of sample display are added into the surface of Ceramic Balls.The quality of coating is usually in the scope of 4.8g to 6.0g coating.The method described in embodiment 18 of use, the average CA loading capacity be determined on these fillers is often liter of filler 6.3g CA.CA loading capacity is usually in the scope of often liter of filler 5.0 to 7.0g CA.
Use the sign display structure feature of SEM and those constitutional featuress shown in Fig. 9 A-D similar.
embodiment 20: the activity research with the pottery of multiple silicon-dioxide/enzyme coating utilizing the catalysis using surface to cause
There is for screening the activity of the sample of multiple coatings of the CA containing polysilicates/silicone materials, utilize small-scale single pass reactors as described in example 17 above.
As shown in Figure 11, the quality that the catalysis by utilizing surface to cause increases coating creates the CO demonstrating brilliance 2the sample of conversion capability.Use these methods prepare and containing 5.96g coating (about 6% enzyme) sample display K gvalue is 0.18mmol/sm 2kPa, this value corresponds to transformation efficiency and 10 times of speed enhancing multipliers of almost 80%.
Above activity is recorded in short-term test (namely 30 minutes).For studying this sustainability transformed and qualification stable state conversion rate, in SPR, carry out test run in 24 hours.These the results are shown in Figure 12.
Above-mentioned sample demonstrates overall mass transfer coefficient (K g) be 0.180mmol/sm 2kPa, this corresponds to CO2 trapping (see Figure 12) of about 80%.This corresponds to over uncoated Ceramic Balls (K g=0.0145mmol/sm 2kPa) about 12.4 times of (K are strengthened g/ K gblank).The working time of going through nearly 24 hours observes lasting CO 2conversion rate.
embodiment 21: the long period of activity research of the Ceramic Balls with polysilicates-silicone multipolymer coating using closed loop continuous flow reactor to carry out.
This embodiment tests the activity of the solid carrier of coating for a long time under the condition by hot steam stripping regeneration resorber solvent.
The ring-closure reaction device (CLR) run under being used in Continuous Flow.Graphically depicting in Fig. 2 of system.Absorption tower is high 78.5cm, internal diameter 5/8 " with Ceramic Balls fill counter-current tower.Resorber solution is 0.8M/1.2M K 2cO 3/ KHCO 3damping fluid (under pH=10.0).
Solution in resorber circulates from the top of tower with the speed control of 20 ml/min.Comprise 15%CO 2(use N 2counterweight) gas upwards flow (400 ml/min) from the bottom of tower.Thermal jacket is seated on tower to maintain the solution temperature about 45 DEG C in resorber.
Use the CO of the output of monitoring tower 2the non-dispersive infrared detector (NDIR) of gas comes CO 2conversion is carried out quantitatively.Export the CO of gas 2content is compared to the CO of feed gas 2difference between content is for calculating uptake rate.
Wherein be embedded with the sample of the ceramic filling material of the polysilicates-silicone copolymer coating coating of carbonic anhydrase with three layers according to the program preparation of setting forth in embodiment 18.The activity 366 days of study sample in CLR.The result of this analysis is presented in Figure 13.
It is 75% that first 76 days average conversions are gone through in sample display, and this corresponds to average K gfor 0.143mmol/sm 2kPa and average enhancing multiplier are 9.9 (K g/ K gblank).Study by CLR the result obtained to indicate by 1.19 × 10 -5the CA of mol goes through the CO transformed for 100 days 2amount be 10.9kg.This corresponds to total turnover number (CO 2mole number/CA mole number) be about 2,360 ten thousand.
After 366 days, according to the total turnover number (CO calculating above sample 2mole number/CA mole number) be about 5,890 ten thousand.
embodiment 22: long-term enzyme retains research
Wherein be embedded with the sample of the ceramic filling material of the polysilicates-silicone copolymer coating coating of carbonic anhydrase with three layers according to the program preparation of setting forth in embodiment 18.
Sample is seated in high 78.5cm, internal diameter 5/8 " with Ceramic Balls fill tower in.Resorber solution is 0.8M/1.2M KHCO 3/ K 2cO 3solution (pH ≈ 10), and apply from the top of tower with speed control (20 ml/min).Resorber solution is from reservoir continuous circulation on sample.
Ultraviolet-visible (UV-vis) spectrum analysis is used to go through time measurement enzyme loss (i.e. leaching) of 42 days relative to the working curve of preparation.Enzyme loss amount during test period is calculated as percent loss.The results are shown in Figure 14 of this calculating.
The result presented in Figure 13 and 14 clearly states the biocatalysis coating described in the application and maintains CO 2conversion and enzyme retain the especially long time.
embodiment 23: at contaminant trace species SO 2and NO 2to the activity research of the Ceramic Balls with polysilicates-silicone multipolymer coating under existence.
Wherein be embedded with the sample of the ceramic filling material of the polysilicates-silicone copolymer coating coating of carbonic anhydrase with three layers according to the program preparation of setting forth in embodiment 18.
70mL tower is filled with the immobilized enzyme of the polysilicates/polysiloxane coating materials be configured on 3.6mm Tipton Ball-type packing under the air-flow of 0.4SLPM.
Initial gas charging is by the 15%CO of nitrogen counterweight 2(Figure 15; With going through ~ the first blue trace display of 1 day).
Then feed gas is converted to and use 20ppm NO 2with 20ppm SO 2fusion by the 15%CO of nitrogen counterweight 2.
The green trace display going through 5 days of the properties of sample Figure 15 under this feed gas.
Then feed gas is converted back original 15%CO 2(by nitrogen counterweight), this last blue trace (~ the 6 to 7 day) with Figure 15 shows.
This result illustrates and is being present in the trace NO in burning rear pass gas 2and SO 2there is the lower suppression lacked immobilization carbonic anhydrase.
embodiment 24: use coal combustion flue gas to the activity research undertaken by the Ceramic Balls of polysilicates-silicone multipolymer coating.
Wherein be embedded with two samples of the ceramic filling material of the polysilicates-silicone copolymer coating coating of carbonic anhydrase with three layers according to the program preparation of setting forth in embodiment 18.
Test cell by operate under 200sccm air-flow containing 5/8 of the immobilized enzyme be coated on 3.6mm Tipton ceramic spherical filler " internal diameter absorption tower forms.
Use at room temperature operate between 2SLPM and 5SLPM 3 " diameter air stripper bubble-plate column, salt of wormwood solvent maintains the constant feed pH of ~ 10.
Combustion gases are obtained by Fen He basin, Wyoming (Wyoming Powder River Basin) sub-bituminous coal and filter and condensate moisture and after removing in feed-in unit at baghouse (bag-house).
Measuring mercury content is 3.06 μ g/m 3total Hg content, wherein 1.07 μ g/m 3in Hg + 2form and 1.99 μ g/m 3in Hg 0form.
Go through the time length of experiment, the CO of stack gas 2component average out to ~ 13.9%.
Two coating Tipton samples repeated are used for the reference test and comparison carried out with bottled clean air mixture the performance of stack gas.Two tests are all analyzed under same operation condition (i.e. 200sccm feed gas).
As can finding in figure 16, go through whole experimentation, the sample standing stack gas with reference to sample same show good, the CO between trapping 90% and 95% 2charging.
embodiment 25: with silicon ester primer coating treatment S ulzer structuring filling
With previously described for similar with the stainless literature procedure of tetraethylorthosilicise process, load 97.5mL ethanol, 97.5mL tetraethylorthosilicise and 13.7mL2M NH to 500mL Pyrex bulb 4oH.
Make reaction mixture aging minimum 30 minutes, at described time durations, soliquid becomes obvious.
By above mixture spray application in 2 " tower diameter Sulzer on 7 unit of 500X structuring filling.Scalable is to adapt to the packing material with different tower diameter and either large or small surface-area.
After spray application, at room temperature dry sample 30 minutes, then solidifies at elevated temperatures, and wherein temperature variation is the soaring process of 60 DEG C-350 DEG C gone through 2 hours, within 1 hour and last 1 hour at 450 DEG C, rises to 650 DEG C from 550 DEG C.
After solidification, coating to room temperature and then gentle washing is cooled.
Repeat described process twice before the use again and drying.
embodiment 26: use methanol dilution method spray application Sulzer structuring filling with the polysiloxane/polysilicates coating of preparation containing immobilization carbonic anhydrase.
According to embodiment 25 four ortho-silicate pre-treatment Sulzer 500X, 2 " three unit of tower diameter structure filler are to provide primer coating.
In some cases, before deposition polysiloxane/polysilicates immobilization material, filler is immersed in 100mM NH 4also dry in F.In some cases, this pre-treatment is not used.
The 150mg/mL carbonic anhydrase solution (as described in example 1 above) of 16.2mL and the CTAB of 675mg is loaded to 400mL beaker.In some cases, CTAB is not used.Inclusion is mixed until CTAB dissolves completely by magnetic force or mechanically mixing.
With vigorous stirring, slowly add containing tetramethylorthosilicate (17.5mL; 118m mol), silanol stopped polydimethylsiloxane (14.8mL; 26mmol) be preced with the monomer solution of-6 (4.05g) with 18-and improve mixing rate.The adulterant of alkyl-Trimethoxy silane and PEG source property trialkoxy silane has also used similar approach to produce.
Once mixture forms the emulsion (water-in-oil) of good distribution, namely add 63.5mL methyl alcohol in beaker, add 74 μ L NH at once subsequently 4f catalyzer.Then 6 points, vigorous stirring mixture 15 seconds.Mixing time easily can be changed based on the amount of used catalyst and reaction scale.
Then coating solution to be transferred in the heavy body low pressure (HVLP) fog gun (Aeropro, G6600-25) operated under 40psi and to be deposited on structuring filling.The fog gun of other type can be utilized.In addition, the mixture with this character is also deposited by immersion coating, roll-type coating or flow coating.
In coating procedure, structurizing packing material can sheet form horizontally disposed or be hung vertically on suspension hook.
After coating, sample is coated, at room temperature by its drying 30 minutes to 1 hour.Then sample is transferred in 55 DEG C and continues 1 hour, and then make temperature ramps to 75 DEG C, continue 2 hours.Different solidification value and time can be utilized.Method described herein has produced optimum Activity Results.
After the first coating deposition, the same preparation that scale increases by 1.5 times deposits the second coating for using same procedure and program curing.The volume of needs to multiple coating and spray solution used can be determined based on desired properties and film thickness.The use of three coatings provides optimal performance in test macro as herein described.
After the second coating, scale increases the same preparation of 2 times for using same procedure to deposit the 3rd coating.
After the 3rd coating, solidified sample 24 hours at 55 DEG C and then at 75 DEG C solidify 72 hours.Again, the different versions of set time can optionally in application-specific.
After final solidification, within 48 to 96 hours, washed and hydration Sulzer by submergence in excessive aqueous buffer solution 500X, 2 " Individual cells of tower size filler.Usually, utilize at 0.8M/1.2M K 2cO 3/ KHCO 3submergence 72 hours in damping fluid (under pH=10.0), but, can optionally utilize different aqueous buffer solution, pH and hydration time.
During washing hydro-combination process or afterwards, from dipping solution remove aliquots containig and enzyme in volumetric soiutions to measure the enzyme reservation of immobilization matrix.
After abundant hydration, by coated and thin slice is in position assembled into by their spot welding complete 2 with scraping band " diameter structure packing section.Then 2 are being equipped with " analytic sample in one of some reactors on absorption tower.
In mass, the enzyme/monomers/water ratios of the sol preparation of above display is 1: 15: 5.This ratio by increasing or reduce the amount of monomer (i.e. tetramethylorthosilicate and poly-(dimethyl siloxane)), or is easily changed by the volume increasing or reduce the proenzyme liquid be added in sol preparation.In addition, in sol preparation, the above ratio being shown as the monomer/hydrophilic additive of 45: 1 (with molar basis) can change in a similar fashion.
This program is also for applying Sulzer 500X and being also deposited on the top of other base paint comprising ceramic bases coating.
embodiment 27: use alcohol dilution method spray application Sulzer structuring filling with the polysiloxane/polysilicates coating of preparation containing immobilization carbonic anhydrase.
In an exemplary program, in 1L flat-bottomed flange reaction flask, load 150mg/mL carbonic anhydrase reserve solution A (as described in example 1 above) of 7.2mL.
In this enzyme solution, add 0.30g cetyl trimethylammonium bromide (CTAB, 0.8mmol) and stir with magnetic stirring bar or mechanical stirrer and dissolve completely to reach.
Then, add with vigorous stirring containing tetramethylorthosilicate (7.8mL, 52mmol), silanol stopped poly-(dimethyl siloxane) (average M w=550; 6.6mL) be preced with the monomer solution of-6-ether (1.8g, 6.6mmol) with 18-.
After effectively disperseing and emulsion is formed subsequently, add the 0.1M NH of 9.0mL 4f is in stirring the mixture.Mixture gets started and becomes opaque, and adds 27mL reagent alcohol (90% ethanol, 5% methyl alcohol, 5% Virahol) fast with vigorous stirring.
After 10-15 second, this mixture starts thickening, and second aliquots containig of under agitation adding 7.5mL reagent alcohol is to contribute to shifting mixture.
Then by volume this mixture is divided into two.Half is transferred in the heavy body low pressure (HVLP) fog gun (Aeropro, G6600-25) operated under 40psi.Whole inclusion of fog gun hopper are all sparged 8.75 " long stainless steel structure filler (Sulzer 500X, 2 " tower diameter) section side on, described packing section is horizontally disposed or be hung vertically on suspension hook with sheet form.
Make this polysilicates-silicone coating at room temperature dry 20 minutes and then overturn thin slice and spray with second half mixture.
Make this coating at room temperature dry 30 minutes and to be then seated in 55 DEG C of baking ovens dry 1 hour.Follow above program and increase by 1.5 times of lower interpolation second coatings in proportion at often kind of reagent.
Follow above formula and increase by 2.0 times of lower interpolations the 3rd coating (and being final coating) in proportion at often kind of reagent.After the both sides of filler are all by spraying, make coating at room temperature dry 30 minutes and be then seated in 55 DEG C of baking ovens to spend the night with dried/cured.Then it is transferred in 75 DEG C of baking ovens and solidifies 72 hours.
One substituting cure cycle research be utilize dry overnight at room temperature after coating 1 and 2, sometimes before next coating of interpolation at 55 DEG C dry 1 hour morning next day.After the 3rd (finally) coating, at room temperature dry sample spends the night, at 75 DEG C dry 72 hours subsequently.Also other change in time of drying and temperature is successfully adopted.
After completing cure cycle, remove thin slice from baking oven and put the 0.8M/1.2M K into known volume 2cO 3/ KHCO 3water to merge in the couveuse put and be at 45 DEG C at least 3 days in damping fluid (under pH=10.0).Hydration also can realize under other temperature and time comprising room temperature, but herein preferably 45 DEG C continue at least 3 days.
Regularly obtain aliquots containig from this solution to retain to assess enzyme.
After abundant hydration, by being with coated with scraping and thin slice be in position assembled into complete 2 by their spot welding " diameter structure packing section.Then 2 are being equipped with " analytic sample in one of some reactors on absorption tower.
This program also has 4 for coating " tower diameter and 8 " Sulzer of tower diameter 500X, and the top being also deposited on other base paint comprising ceramic bases coating.
embodiment 28: the Sulzer utilizing silicon-dioxide/enzyme coating the activity research of 500X structuring filling
Two separate payments, i.e. test 2 in ring-closure reaction device CLR and structuring filling test board (SPTS) " Sulzer of coating of tower diameter the activity of 500X sample.
Use in this test and to be shown in Fig. 2 and operational condition is described in the ring-closure reaction device system in embodiment 21.Make a change to adapt to 2 " structuring filling, comprise and use high 91.4cm, diameter 2 " tower of inch.Thermal jacket is seated on tower and is approximately 45 DEG C with the solution temperature maintained in resorber.The all samples tested in CLR all carries out this measure at 45 DEG C.
For single hop 2 in CLR " typical operation conditions of structuring filling is as follows: with the top pumping resorber solution (45 DEG C) of speed control (218 ml/min) from tower.Comprise 15%CO 2(use N 2counterweight) gas move up (2.18SLPM) from the bottom of tower.SPTS can to nearly four ~ 2 " diameter structure packed absorber or ~ 4 " structuring filling absorption tower carries out continuous closed-loop test.SPTS utilizes warm air stripping to carry out regenerated solvent.
Absorption tower in SPTS is with 2 " structuring filling fill high 106.6cm, internal diameter 21/8 inch counter-current tower.The tower of high 106.6cm, internal diameter 3.95 inches is used for 4 " structuring filling sample.Resorber solution is 0.8M/1.2M K 2cO 3/ KHCO 3damping fluid (under pH=10.0).
All tests in SPTS system are all at room temperature carried out.
2 " the liquids and gases flow velocity of structuring filling is identical with above-mentioned flow velocity.4 " the liquids and gases flow velocity of structuring filling is as follows; With 1200 ml/min pumping resorber solution the bottom of gas from tower under 8SLPM upwards flowed.
Use monitoring at the CO of the output of tower 2the non-dispersive infrared detector (NDIR) of gas comes the CO in two systems 2conversion is carried out quantitatively.Export the CO of gas 2content is compared to the CO of feed gas 2difference between content is for calculating uptake rate.
Table 3 shows the activity of the sample according to embodiment 26 and 27 preparation tested in SPTS.On average, be proved can with 0.133mmol/s-m for sample 2the average K of-kPa gtransform 70%CO 2.With with 0.0118mmol/s-m 2the K of-kPa gtransform average 14%CO 2have 2 " exposed (uncoated) Sulzer of tower diameter the comparison of 500X sample provides the mean rate constant multiplier of 11.19, and described multiplier is for determining that coating is at conversion CO 2measuring of effect of aspect.
table 3: to having 2 in SPTS " Sulzer of the silicon-dioxide of tower diameter/enzyme coating the analysis of 500X sample.
For test has 2 " Sulzer of the coating of tower diameter the long period of activity of 500X sample, uses CLR reactor usually.In fig. 17, in CLR, analyze prepare according to embodiment 26 2 " sample that applies 3 days.Gained sample is presented at average K in this period gfor 0.12mmol/s-m 2-kPa.
For test CO 2associating between transformation efficiency with enzyme loading capacity (film thickness), with the program similar with the program described in embodiment 26,0.051% catalyzer (mol ratio of catalyzer and reactive monomer (TMOS and PDMS)) is used to prepare three samples.The single coating of described sample respectively containing silicon-dioxide/enzyme immobilization matrix (CA of often liter of reactor volume 1.18g), two coatings (CA of often liter of 2.44g) and three coatings (CA of often liter of 5.16g).As shown in Figure 18, sample activity increases with the enzyme loading capacity in sample and increases.
In Figure 19, in CLR, analyze prepare according to embodiment 27 2 " sample that applies 3 days.The K in period of 3 days is gone through in display gbe continuously 0.12mmol/s-m 2-kPa.Sample is presented at this degradation in period and can ignores.
embodiment 29: use the epoxide tackiness agent coating of adhesion porous xerogel powder to have 2 " Sulzer of tower diameter 500X
In an exemplary program, prepare 100g two-component epoxy (Pro-Poxy200) and be added in shallow slot.
This epoxide methyl alcohol (75mL) is diluted and fully mixes to homogenize.By 8.75 " long stainless steel structure filler (Sulzer 500X; 2 " tower diameter, amount to 7 thin slices) individual flakes of section is immersed in the epoxy hybrids of dilution, and then with a kind of dry gel powder dusting using < 500 micron diameter to sieve to prepare according to embodiment 1 with complete cover ring oxide skin.
The dry gel powder loading capacity on sample is determined by the mass discrepancy of dry gel powder before and after coating procedure.
This method is for being adhered to the surface of stainless steel structure packing material and the random packing material of pottery by the representative powder from embodiment 1,3 and 7.
Then thin slice is suspended on at room temperature dry 3 hours on the suspension hook in stink cupboard, and is then transferred to 55 DEG C of baking ovens and spends the night epoxide curing.
After completing cure cycle, remove thin slice from baking oven and put the 0.8M/1.2M K into known volume 2cO 3/ KHCO 3few 3 days are hydrated in damping fluid (under pH=10.0).
Regularly obtain aliquots containig from this storage solutions to retain to assess enzyme.
After abundant hydration, by coated and thin slice is in position assembled into by their spot welding complete 2 with scraping band " diameter structure packing section.
Then 2 are being equipped with " analytic sample in one of some reactors on absorption tower.
embodiment 30: what use the epoxide tackiness agent coating of adhesion porous xerogel powder has 2 " Sulzer of tower diameter the active testing that 500X sample carries out
In some cases, CLR has 2 for use in testing for what use the epoxide tackiness agent coating of adhesion porous xerogel powder according to the method described in embodiment 29 " Sulzer of the coating of tower diameter the activity of 500X sample.
In fig. 20, use epoxide tackiness agent to make the dry gel powder prepared according to the experimental arrangement described in embodiment 3 be adhered to Sulzer filler and test active in CLR.Sample shows average K gfor 0.051mmol/s-m 2-kPa, this corresponds to over 3.2 times of blank enhancings.
In figure 21, use epoxide tackiness agent to make the dry gel powder prepared according to the experimental arrangement described in embodiment 7 be adhered to Sulzer filler and test active in CLR.This sample shows average K gfor 0.113mmol/s-m 2-kPa, this corresponds to over the enhancing of blank 7.1 times.
In fig. 22, use epoxide tackiness agent to make the dry gel powder prepared according to the experimental arrangement described in embodiment 1 be adhered to Sulzer filler and test active in CLR.Sample shows average K gfor 0.070mmol/s-m 2-kPa, this corresponds to over 4.4 times of blank enhancings.
Above embodiment display business tackiness agent can be used for xerogel particles is incorporated on solid carrier in enzymatic carbon capture method.
When introducing the key element of the present invention or its preferred embodiment, article "/one (a, an) " and " described (the, said) " mean to there is one or more key element.Term " comprises ", " comprising " and " having " means comprising property and mean other key element that can exist except listed elements.
In view of the above, be that some targets of the present invention are reached and obtain other advantageous results by visible.
Because various change can be made to above product and method without departing from the scope of the invention, so all items that intention contains in the above description and shows in alterations all should be interpreted as illustrative but not have restrictive, sense.

Claims (97)

1. an immobilized enzyme, it comprises
Enzyme; And
Immobilization material;
Wherein said enzyme is embedded in described immobilization material and described immobilization material is obtained by colloidal sol and catalyst reaction, described colloidal sol comprises (i) organoalkoxysilane or organotrialkoxysilane or metasilicic acid ester, (ii) poly-(silicone), and (iii) enzyme.
2. immobilized enzyme as claimed in claim 1, wherein said poly-(silicone) comprises poly-(siloxanes).
3. immobilized enzyme as claimed in claim 1 or 2, wherein said colloidal sol comprises hydrophilic additive further.
4. one kind comprises the upholder carrier of the coating of the polysilicates-silicone multipolymer of immobilized biocatalyst; Described polysilicates-silicone multipolymer is adhered to solid carrier by coating of adhering.
5. the carrier of coating as claimed in claim 4, wherein said biological catalyst comprises enzyme.
6. the immobilized enzyme according to any one of claims 1 to 3 and 5 or the carrier of coating, wherein said enzyme comprises lipase, glucose isomerase, nitrilase, glucose oxidase, proteolytic enzyme, carbonic anhydrase, stomach en-, amylase, fungal amylase, maltogenic amylase, cellulase, Sumylact L, esterase, carbohydrase, hemicellulase, pentosanase, zytase, Starch debranching enzyme, beta-glucanase, acetolactate decarboxylase, beta-glucosidase, L-Glutamine deaminase, penicillin acylase, chloroperoxidase, aspartic acid β-decarboxylase, Maltose 4-glucosyltransferase, subtilisin, amino acylase, alcoholdehydrogenase, amino-acid oxidase, phospholipase, urase, Sterol esterase, desulfinase, lignin peroxidase, polygalacturonase, oxydo-reductase, dextranase, glucuroide, tilactase, glucoamylase, maltin, sucrase, saccharase, naringinase, bromeline, ficin, papoid, stomach en-, peptase, rennin, thermolysin, trypsinase, triglyceride level enzyme, stomach proesterase, Phosphoric acid esterase, phytase, Ntn hydrolase, L-Glutamine deaminase, N,O-Diacetylmuramidase, katalaze enzyme, desaturase, peroxidase, lyase, FURAMIC ACID, histidase, transaminase, ligase enzyme, cyclase, racemase, mutase, oxydase, reductase enzyme, lignoenzyme, laccase, chloroperoxidase, haloperoxidase, hydrogenase, nitrogenase, oxynitrilase or its combination.
7. a carrier for coating, it comprises
Solid carrier;
Cambial application composition on the surface of described solid carrier, described application composition comprises polysilicates-silicone multipolymer and hydrophilic additive; And
Be embedded in the biological catalyst of the catalysis hydrated carbon dioxide in described application composition.
8. the immobilized enzyme according to any one of claim 1 to 7 or the carrier of coating, wherein said enzyme or biological catalyst are carbonic anhydrases.
9. the carrier of the coating according to any one of claim 4 to 6 and 8, wherein said adhesion coating comprises polymeric stickers.
10. the carrier of coating as claimed in claim 9, wherein said polymeric stickers comprises urethane polymer, epoxide polymer, resin, cyanoacrylate polymer, methacrylate polymers or its combination.
The carrier of 11. coatings as described in claim 9 or 10, wherein said polymeric stickers comprises polycomponent adhesive polymer.
12. carriers applied as claimed in claim 11, wherein said adhesive polymer comprises two-component epoxy polymkeric substance, two-part urethane polymkeric substance or its combination.
13. carriers applied as claimed in claim 12, wherein said adhesive polymer comprises two-component epoxy polymkeric substance.
The carrier of 14. coatings according to any one of claim 4 to 13, wherein said polysilicates-silicone multipolymer comprises silicon ester-silicone copolymers.
The carrier of 15. coatings according to any one of claim 4 to 14, wherein said application composition is reacted by colloidal sol to obtain, described colloidal sol comprises (i) organoalkoxysilane or organotrialkoxysilane or metasilicic acid ester, (ii) poly-(silicone), (iii) hydrophilic additive, and the biological catalyst of (iv) catalysis hydrated carbon dioxide.
16. carriers applied as claimed in claim 15, wherein said application composition is obtained by colloidal sol and catalyst reaction.
The carrier of 17. coatings as described in claim 15 or 16, wherein said poly-(silicone) is selected from the group be made up of poly-(siloxanes), poly-(silicic acid glyceryl ester) and polysilsesquioxane.
18. carriers applied as claimed in claim 17, wherein said poly-(silicone) comprises poly-(siloxanes).
19. 1 kinds for certainly containing CO 2gas remove CO 2method, described method comprises
Make liquid and contain CO 2gas contact; And the CO making in described liquid 2with the carrier contact of the immobilized enzyme according to any one of claim 7 to 18 or coating with CO as described in catalysis 2hydration also forms the treated liquid comprising hydrogen ion and bicarbonate ion.
20. methods as claimed in claim 19, wherein said liquid is waterborne liquid.
21. 1 kinds for certainly containing CO 2gas remove CO 2the system comprising reaction vessel, described reaction vessel comprises base section containing gas feed and liquid exit, top section containing liquid-inlet and pneumatic outlet and containing the multiple carrier of the coating according to any one of claim 7 to 18 or the middle portion of immobilized enzyme, and described carbonic anhydrase can catalysis CO 2hydration becomes hydrogen ion and bicarbonate ion.
22. according to any one of claim 19 to 21 for from containing CO 2gas remove CO 2method or system, wherein said immobilized enzyme is particulate forms.
23. as claimed in claim 22 for certainly containing CO 2gas remove CO 2system, wherein said immobilized enzyme particle is in the suspension form of suspension of middle portion being in described reaction vessel.
24. according to any one of claim 21 to 23 for from containing CO 2gas remove CO 2system, it comprises the second reaction vessel further, the carrier of described second reaction vessel containing, for example the coating according to any one of claim 7 to 18 or the suspension of immobilized enzyme, wherein said carbonic anhydrase hydrogen ion described in catalysis and described bicarbonate ion can change into CO 2and water.
25. as claimed in claim 24 for certainly containing CO 2gas remove CO 2system, wherein said immobilized enzyme is particulate forms.
26. as described in claim 24 or 25 for from containing CO 2gas remove CO 2system, described second reaction vessel is that hydrogen ion and bicarbonate ion are converted to CO 2with the place residing for water.
27. 1 kinds of methods for the preparation of immobilized enzyme, it comprises:
Mixing (i) organoalkoxysilane or organotrialkoxysilane or metasilicic acid ester, (ii) poly-(silicone), (iii) hydrophilic additive, (iv) carbonic anhydrase, and (v) solvent is to form colloidal sol;
Make described colloidal sol and catalyst exposure to form gel; And
Described gel is solidified at the temperature of about 55 DEG C to about 100 DEG C.
28. methods as claimed in claim 27, wherein said temperature is about 70 DEG C to about 85 DEG C.
29. methods as described in claim 27 or 28, wherein solidify described gel 24 little of 72 hours.
30. 1 kinds of methods for the preparation of the carrier of the coating such as according to any one of claim 7 to 18, it comprises:
Mixing (i) organoalkoxysilane or organotrialkoxysilane or metasilicic acid ester, (ii) poly-(silicone), (iii) hydrophilic additive, (iv) carbonic anhydrase, and (v) solvent is to form colloidal sol;
Make described colloidal sol and catalyst exposure to form gel; And
Make solid carrier and described gel contacts.
31. 1 kinds of methods for the preparation of the carrier of the coating such as according to any one of claim 4 to 6 and 8 to 18, it comprises:
Mixing (i) organoalkoxysilane or organotrialkoxysilane or metasilicic acid ester, (ii) poly-(silicone), (iii) hydrophilic additive, (iv) carbonic anhydrase, and (v) solvent is to form colloidal sol;
Make described colloidal sol and catalyst exposure to form gel;
Dry described gel also forms xerogel particles;
Make solid carrier and described adhesion coating contacts;
The solid carrier with described adhesion coating is made to contact to be formed the carrier of described coating with described xerogel particles.
32. methods as described in claim 30 or 31, wherein said poly-(silicone) comprises poly-(siloxanes).
33. methods as described in claim 30 or 31, it comprises the carrier of dry described gained coating further.
34. methods according to any one of claim 30,32 or 33, it comprises the carrier with applying described in another layer of described gel coating further.
35. methods according to any one of claim 30 to 34, wherein said solvent is water-based.
36. carrier, processing method, system, immobilized enzyme or methods according to any one of claims 1 to 3 and 15 to 35, wherein said organoalkoxysilane is tetramethylorthosilicate, tetraethylorthosilicise, methyl triethyl ortho-silicate, ethyl-trimethyl ortho-silicate, dimethyl diethyl ortho-silicate, silicic acid four glyceryl ester or its combination.
37. carrier, method, system, immobilized enzyme or methods according to any one of claims 1 to 3 and 15 to 36, wherein said organotrialkoxysilane is trimethoxymethylsila,e, trimethoxy ethylsilane or its combination.
38. carrier, method, system, immobilized enzyme or methods as claimed in claim 37, wherein said organoalkoxysilane comprises tetramethylorthosilicate.
39. carrier, method, system, immobilized enzyme or methods according to any one of claims 1 to 3 and 15 to 38, wherein said poly-(silicone) is selected from poly-(siloxanes) by the group of poly-(dimethyl siloxane), poly-(dimethyl siloxane)-altogether-poly-(oxyalkylene) or combinations thereof.
40. carrier, method, system, immobilized enzyme or methods as claimed in claim 39, wherein said poly-(siloxanes) comprises polydimethylsiloxane.
41. carrier, method, system, immobilized enzyme or methods according to any one of claims 1 to 3 and 15 to 40, wherein said poly-(silicone) is silanol stopped.
42. carrier, method, system, immobilized enzyme or methods according to any one of claim 1 and 15 to 41, wherein said hydrophilic additive is poly-(vinyl alcohol), poly-(oxyethane), quaternary ammonium polymer, crown ether, cyclodextrin, tensio-active agent, cetyl trimethylammonium bromide, poly-(1-methyl-4-vinylpridine bromide), poly-(acrylamide-methacryloyl oxygen base ethyMmethylammonium bromide) or its combination.
43. carrier, method, system, immobilized enzyme or methods as claimed in claim 42, wherein said quaternary ammonium polymer is poly-(diallyldimethylammonium chloride), poly-(1-methyl-4-vinylpridine bromide), poly-(acrylamide-methacryloyl oxygen base ethyMmethylammonium bromide) or its combination.
44. carrier, method, system, immobilized enzyme or methods as claimed in claim 43, wherein said quaternary ammonium polymer comprises poly-(diallyldimethylammonium chloride).
45. carrier, method, system, immobilized enzyme or methods according to any one of claim 42 to 44, wherein said cyclodextrin is alpha-cylodextrin, beta-cyclodextrin, γ-cyclodextrin or its combination.
46. carrier, method, system, immobilized enzyme or methods as claimed in claim 45, wherein said cyclodextrin comprises beta-cyclodextrin.
47. carriers according to any one of claim 42 to 46, method, system, immobilized enzyme or method, wherein said tensio-active agent is two (3-D-glucose cocamidopropyl) the courage acid amides (BigCHAP) of N, N-, two (the 3-D-glucose cocamidopropyl) deoxycholamide (deoxidation BigCHAP) of N, N-, Volpo S 10 (Brij35 and Brij 58 P), 2-cyclohexyl methyl-β-D-Maltose glycosides (Cymal-1), 2-cyclohexyl-ethyl-β-D-Maltose glycosides (Cymal-2), cyclohexylpentyl-β-D-Maltose glycosides (Cymal-5), cyclohexylhexyl-β-D-Maltose glycosides (Cymal-6), decyl-β-D-pyrans maltoside, positive dodecyl-β-D-Maltose glycosides, positive hexadecyl-β-D-Maltose glycosides, undecyl-β-D-Maltose glycosides, decyl-β-D-1-thio-pyrylium maltoside, octyl group-β-D-thioglucopyranoside, digitonin, dimethyldecylphosphine oxide, dodecyl dimethyl phosphine, (Octylphenoxy) polyethoxyethanols ( cA630), N-capryloyl-N-METHYL-ALPHA-L-GLUCOSAMINE (MEGA-8), N-nonanoyl-N-METHYL-ALPHA-L-GLUCOSAMINE (MEGA-9), N-decanoyl-N-METHYL-ALPHA-L-GLUCOSAMINE (MEGA-10), polyoxethylene octylphenyl phenol ( p40 surrogate), polyox-yethylene-polyoxypropylene block copolymer ( f-68), PEG-block-poly-(propylene glycol)-block-PEG ( p-123), saponin, SPE-103 ( ), polyoxethylene octylphenyl phenol (such as x-100 and x-114), the polyoxyethylene deriv of Span 20 (such as 20, 40 Hes 80), N, N-dimethyl amino dodecane-N-oxide compound, alcohol ethoxylate ( a7) or its combination.
48. carrier, method, system, immobilized enzyme or methods according to any one of claim 42 to 46, wherein said colloidal sol comprises cetyl trimethylammonium bromide further.
49. carrier, method, system, immobilized enzyme or methods as claimed in claim 47, wherein said tensio-active agent comprises cetyl trimethylammonium bromide (CTAB).
50. carrier, method, system, immobilized enzyme or methods according to any one of claim 42 to 49, wherein said crown ether is 12-crown-4,1,7-diaza-12-crown-4, Isosorbide-5-Nitrae, 8, the 11-tetra-thia ring tetradecane, Isosorbide-5-Nitrae, 8,12-tetraazacyclododecane pentadecane, 15-hat-5,18-hat-6, dibenzo-18 crown-6, two hexamethylenes are-18-hat-6, (18-hat-6)-2 also, 3,11,12-tetracarboxylic acid, 1-azepine-18-hat-6, diaza-18-are preced with-6 or its combination.
51. carrier, method, system, immobilized enzyme or methods as claimed in claim 50, wherein said crown ether comprises 18-hat-6.
52. carrier, method, system, immobilized enzyme or methods according to any one of claim 3 and 15 to 51, wherein said organoalkoxysilane comprises tetramethylorthosilicate, described poly-(siloxanes) comprises polydimethylsiloxane, and described hydrophilic additive comprises crown ether.
53. carrier, method, system, immobilized enzyme or methods according to any one of claim 8 to 52, wherein said carbonic anhydrase is the carbonic anhydrase that kytoplasm carbonic anhydrase, plastosome carbonic anhydrase, the carbonic anhydrase of secretion or film are relevant.
54. carrier, method, system, immobilized enzyme or methods as claimed in claim 53, wherein said carbonic anhydrase is Mammals carbonic anhydrase, plant carbonic anhydrase or microorganism carbonic anhydrase.
55. carrier, method, system, immobilized enzyme or methods as claimed in claim 54, wherein said carbonic anhydrase comprises BCA, people's carbonic anhydrase or microorganism carbonic anhydrase.
56. carrier, method, system, immobilized enzyme or methods as claimed in claim 55, wherein said carbonic anhydrase comprises BCA II and described people's carbonic anhydrase comprises people's carbonic anhydrase IV.
57. carrier, method, system, immobilized enzyme or methods according to any one of claims 1 to 3 and 15 to 56, wherein organoalkoxysilane or organotrialkoxysilane or metasilicic acid ester and the mol ratio of poly-(silicone) be about 1: 1, about 2: 1, about 3: 1, about 4: 1, about 5: 1, about 6: 1, about 7: 1, about 8: 1, about 10: 1, about 12: 1, about 15: 1 or about 20: 1.
58. carrier, method, system, immobilized enzyme or methods according to any one of claims 1 to 3 and 15 to 56, wherein organoalkoxysilane or organotrialkoxysilane or metasilicic acid ester and the mol ratio of poly-(silicone) are about 1: 1 to about 20: 1, about 2: 1 to about 8: 1 or about 3: 1 to about 5: 1.
59. carrier, method, system or methods according to any one of claim 4 to 58, wherein said solid carrier is packing material or the structurizing packing material of commercially available acquisition.
60. carrier, method, system or methods according to any one of claim 4 to 58, wherein said solid carrier is the random packing material of commercially available acquisition.
61. carrier, method, system or methods as described in claim 59 or 60, wherein said solid carrier comprises stupalith.
62. carrier, method, system or methods as claimed in claim 61, wherein said solid carrier is Ceramic Balls.
63. carrier, method, system or methods as described in claim 59 or 60, wherein said solid carrier comprises stainless steel.
64. carrier, method, system, immobilized enzyme or methods according to any one of claim 1 to 63, the total pore volume of wherein said coating or immobilization material is at least about 3 μ L/g to 500 μ L/g.
65. carrier, method, system, immobilized enzyme or methods according to any one of claim 1 to 64, the surface-area of wherein said coating or immobilization material is at least about 1m 2/ g, at least about 5m 2/ g, at least about 10m 2/ g, at least about 20m 2/ g, at least about 30m 2/ g, at least about 40m 2/ g, at least about 50m 2/ g, at least about 60m 2/ g, at least about 70m 2/ g, at least about 80m 2/ g, at least about 90m 2/ g, at least about 100m 2/ g, at least about 150m 2/ g, at least about 200m 2/ g or at least about 300m 2/ g.
66. carrier, method, system, immobilized enzyme or methods according to any one of claim 1 to 64, the surface-area of wherein said coating or immobilization material is about 1m 2/ g to about 400m 2/ g, about 5m 2/ g to about 300m 2/ g, about 10 are to about 150m 2/ g or about 15 is to about 100m 2/ g.
67. carrier, method, system, immobilized enzyme or methods according to any one of claim 1 to 66, the average cell size of wherein said coating or immobilization material is about 2nm to about 80nm.
68. carrier, method, system or methods according to any one of claim 4 to 67, it comprises coating described in one or more layers, and wherein carbonic anhydrase or enzyme are fixed by each layer of being embedded in described coating.
69. carrier, method or systems according to any one of claim 4 to 68, wherein said coating is covalently attached to described solid carrier.
70. carrier, method, system, immobilized enzyme or methods according to any one of claims 1 to 3 and 15 to 69, wherein said catalyzer is Neutral ammonium fluoride, Sodium Fluoride, ammonium hydroxide, sodium hydroxide or its combination.
71. carrier, method, system, immobilized enzyme or methods as described in claim 70, wherein said catalyzer comprises Neutral ammonium fluoride.
72. carrier, method, system, immobilized enzyme or methods according to any one of claim 3 and 15 to 71, wherein the mol ratio of organoalkoxysilane or organoalkoxysilane or metasilicic acid ester and hydrophilic additive be about 48: 1, about 36: 1, about 24: 1, about 12: 1 or about 4: 1.
73. carrier, method, system, immobilized enzyme or methods according to any one of claim 3 and 15 to 71, wherein the mol ratio of organoalkoxysilane or organoalkoxysilane or metasilicic acid ester and hydrophilic additive is about 4: 1 to about 60: 1, about 15: 1 to about 45: 1 or about 30: 1 to about 40: 1.
74. carrier, method, system, immobilized enzyme or methods according to any one of claim 3 and 15 to 73, wherein poly-(silicone) and the mol ratio of hydrophilic additive be about 12: 1, about 9: 1, about 6: 1, about 3: 1 or about 1: 1.
75. carrier, method, system, immobilized enzyme or methods according to any one of claim 3 and 15 to 73, wherein poly-(silicone) and the mol ratio of hydrophilic additive be about 1: 1 to about 30: 1, about 2: 1 to about 20: 1, about 5: 1 to about 15: 1, about 6: 1 to about 12: 1 or about 8: 1 to about 10: 1.
76. carrier, method, system, immobilized enzyme or methods according to any one of claim 8 and 15 to 75, wherein the mol ratio of organoalkoxysilane or organoalkoxysilane and carbonic anhydrase is about 1300: 1.
77. carrier, method, system, immobilized enzyme or methods according to any one of claim 8 and 15 to 75, wherein the mol ratio of organoalkoxysilane or organoalkoxysilane or metasilicic acid ester and carbonic anhydrase is about 4000: 1 to about 600: 1.
78. carrier, method, system, immobilized enzyme or methods according to any one of claim 8 and 15 to 77, wherein poly-(silicone) is about 325: 1 with the mol ratio of carbonic anhydrase.
79. carrier, method, system, immobilized enzyme or methods according to any one of claim 8 and 15 to 77, wherein poly-(silicone) is about 1000: 1 to about 160: 1 with the mol ratio of carbonic anhydrase.
80. carrier, method, system, immobilized enzyme or methods according to any one of claims 1 to 3 and 15 to 79, wherein said colloidal sol comprises the dilute solution containing described organoalkoxysilane and poly-(silicone).
81. carrier, method, system, immobilized enzyme or methods as described in claim 80, the amount of the organoalkoxysilane in wherein said dilute solution is at least about 10 % by weight, at least about 20 % by weight, at least about 30 % by weight, at least about 40 % by weight or at least about 50 % by weight.
82. carrier, method, system, immobilized enzyme or methods as described in claim 80, the amount of the organoalkoxysilane in wherein said dilute solution is about 5 % by weight to about 50 % by weight, about 10 % by weight to about 40 % by weight or about 20 % by weight to about 30 % by weight.
83. carrier, method, system, immobilized enzyme or methods according to any one of claim 80 to 82, the amount of poly-(silicone) in wherein said dilute solution is at least about 2.5 % by weight, at least about 5 % by weight, at least about 7.5 % by weight or at least about 12.5 % by weight.
84. carrier, method, system, immobilized enzyme or methods according to any one of claim 80 to 82, the amount of poly-(silicone) in wherein said dilute solution is about 1% to about 20%, about 2.5% to about 15%, about 5% to about 12.5% or about 5% to about 7.5%.
85. carrier, method, system, immobilized enzyme or methods according to any one of claim 80 to 84, wherein said dilute solution comprises organic solvent.
86. carrier, method, system, immobilized enzyme or methods as described in claim 85, wherein said organic solvent comprises alcohol.
87. methods according to any one of claim 30 and 32 to 86, wherein said solid carrier uses described gel coating by immersion coating, rotary coating, spray application, roll-type coating or submergence coating.
88. methods as described in claim 87, wherein said solid carrier is applied by submergence.
89. methods as described in claim 88, wherein said submergence coating is carried out under high shear.
90. methods according to any one of claim 30 and 32 to 89, wherein made described solid carrier contact with etchant solution before with described gel coating.
91. methods as described in claim 90, wherein said etchant solution comprises acid.
92. methods as described in claim 91, wherein said acid is hydrogen fluoride.
93. methods as described in claim 91 or 92, it comprises described solid carrier is contacted with the etchant solution comprising oxygenant rapid further.
94. methods as described in claim 93, wherein said etchant solution comprises the oxygenant being selected from the group be made up of hydrogen peroxide, ammonium hydroxide and composition thereof.
95. methods as described in claim 94, wherein said etchant solution comprises hydrogen peroxide and ammonium hydroxide with the mass ratio of about 1: 4 to about 4: 1.
The carrier of 96. 1 kinds of coatings, it produces according to the method according to any one of claim 30 to 95.
97. carrier, method, system or methods according to any one of claim 7 to 96, wherein the described biological catalyst of catalysis hydrated carbon dioxide be enzyme, ribozyme, ribodesose enzyme, enzyme mimics, can the organic or inorganic compound of catalysis hydrated carbon dioxide or its combination.
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